99
* O
o
* > MO
we o
a
wff.
*S
o
introduction to
oo H
MOLECULAR
SPECTROSCOPY
4
kctwiHi
G. M.
BARROW
Ccu U.C.
/">
//<
Introduction to
MOLECULAR SPECTROSCOPY
ufY^/^Mr^f*"
n n np
(P*
Introduction to
M O
LONDON
KOGAKUSHA COMPANY,
TOKYO
LTD.
n n n nnnnnnrn
R
S C
P Y
GORDON
M.
BARROW
I96L
manufacture and export from Japan. This book cannot be reexported from the country to which it is consigned by Kogakusha Co.,
Ltd. or by McGrawHill Book
Company,
Inc.
or any of
its
subsidiaries.
I
Copyright
1962
Inc.
by
the
McGrawHill
reserved.
Book Company,
All
rights
This book, or parts thereof, may not be reproduced in any form without permission
of the publishers.
Number 6212478
Tosho Printing
Co., Ltd.,
Tokyo, Japan
PREFACE
who
Both organic and inorganic chemists make use spectrometers as if they were standard tools
chemists base
spectroscopy.
and
ultraviolet
of the trade.
Analytical
of
many
on the methods
Furthermore, almost
chemists
make
frequent use of
much
of this
One
with
can,
it is
true,
make very
or no understanding of the
way
in
trum
the
is
not understood.
The tendency
of
way in many
chemists, who are not molecular spectroscopists, to proceed with this lack of appreciation for the elementary theory of molecular spectroscopy
persists, in part,
This book
gap between the very cursory treatment of spectroscopy generally given in undergraduate textbooks and the detailed treatments written for the specialist and research
is,
worker that are given in books in the various areas of molecular spectroscopy. The reader will here be provided with the basic theory which makes understandable the relationship of the amount and wavelength of
by a sample and the properties of the moleThis introduction should not only allow the organic, inorganic, or analytical chemist to make surer use of spectroscopy as a
cules of the sample.
vi
PREFACE
tool,
is
but should also provide that comfortable feeling of knowing "what happening" when spectroscopic techniques, or results obtained by these
No special background is necessary for the study of this book. Although the Schrodinger wave equation is introduced and simple problems to illustrate its relation to quantities that are important in spectroscopy are solved, no prior knowledge of quantum mechanics is assumed.
known as "group theory" is given Again no methods of group theory. and some analyses are based on the quantum The use of necessary. is previous knowledge of this subject mechanics and group theory is carefully confined to areas of specific value
In a similar way, some of the theory
in this introduction to spectroscopy.
The
level of
treatment
is
main
many
open up. This introduction to molecular spectroscopy will show how molecular spectra can be interpreted in terms of molecular behavior and how, from such interpretations, molecular properties can be obtained. The level of understanding of the theory of molecular spectroscopy that this book
seeks to achieve
is
that from which the student can enter into the special
much
two important
molecular spectroscopy books, frequently referred to throughout the book, by G. Herzberg. It is hoped that the student will be able to under
stand and appreciate advanced and current spectroscopic material if, after studying this book, he pays some additional attention to the details
and nomenclature surrounding a particular spectroscopic subject. With this background the inorganic chemist should, for example, be able to appreciate the very important guides to the nature of bonding in coordination compounds that are now being based, to a large extent, on spectroscopic results.
The organic
be able to make increased use of the information on the nature and energies of excited states that are being discovered and analyzed by the
spectroscopist.
The problems
of selection of material
and depth
of
treatment are,
relative
of course, considerable in
Judgement as to the
PREFACE
vii
and electronic spectroscopy that are generally of interest to chemists. Several sections are concerned in some detail with subjects that are perhaps of special rather than general interest. These sections, marked with an asterisk, can be omitted without destroying the continuity of
the book.
I
would
like to express
my
appreciation to
my
colleagues, Dr.
Wm.
Thompson, and to the graduate students at Case Institute, Mrs. Carol Haberman, Miss Kim Vo, and Mr. I. Chu, for the assistance they have given me by carefully working through
E.
many
am
also indebted to
my
wife,
improvements that she made in the style tion and to Mrs. Julia Dasch for typing the manuscript.
Harriet, for the
of the presenta
Gordon
M. Barrow
CONTENTS
Preface
v
INTRODUCTION
Classifications of Spectroscopy
1
7
7
The Recognition
of
Quantum
Restrictions
12
13
of the
Hydrogen Atom
11
of Particles
14
15
Problem
14
17
16
17
Normalization of
Orthogonality
Wave
Functions
18
18
19
Symmetry
Properties of
Wave
Functions
21
20
110
The Boltzmann
Distribution
23 25
Chapter
OF A DIATOMIC MOLECULE
The
(Classical)
26
of
22
The Vibrations
Spring (Classical)
23
Chemical
CONTENTS
24
The Quantummechanical
monic Oscillator
37
25
Molecules
26
40
of Molecular
The Anharmonicity
Vibrations
43
47
Chapter
The Rotation
(Classical)
of a Linear
System
System (Quantum
53
48
of a Linear
32
The Rotation
Mechanical)
50
33 34
Molecules
35
54
57
Chapter
THE ABSORPTION
41
61
42
43
The
66
70
The
72
Coefficient for a
Transition of a Particle in a
47 48
Box
74 76
Coefficient for
76
49
The
Intensities of Absorption
Bands due to
Electronic Transitions
80
83
Chapter
ROTATIONAL SPECTRA
51
52
The Stark
Spectra
89
53
Nuclearspin
54
The
Positive
Wave
CONTENTS
55
xi
Weight
98
of
Homonuclear Linear
of
Molecules
56
Symmetrictop Symmetrictop
104
57
Selection Rules
and Spectra
of
Molecules
58
106
Symmetrictop Molecules
59
109
510
Chapter
of Independent Vibrations of a
Polyatomic Molecule
62
of
115
116
63
122
64
The Symmetry
Coordinates
Properties of
Normal
125
131
Chapter
ROTATIONVIBRATION SPECTRA
71
72
The Relative
Intensities of the
a RotationVibration Absorption
73 74
Bands
of Linear Molecules
142
146
75 76
77
Bands
of
Symmetrictop Molecules
149
Chapter
82
83
Symmetry
168
84
The Nature
Group
172
xii
CONTENTS
85 86
87
as a
Group
174
Representations of a Group
175 179
88
The
Vectors
89
181
Characters of Representations
Classes
183
810
811
186
188
812
The Characters
190
813
of Various
814 815
195
198
Group Vibrations
Chapter
202
for
92
for a
93
Use
of Lagrange's
Equation in Molecular207
of a Linear
vibration Problems
94
208
95 96
Use
of
Symmetry
in Vibrational
Problems
218
213
Matrix by a Vectorial
in Wilson's
98
Use
Chapter 10
230
of Electronic
102
238
103
104
Atoms
244
251
105
260
CONTENTS
106
xiii
Diatomic Molecules
261 264
Chapter
1 1
266
112
Bands
113
271
114
Systems
115
279
Compounds
116
289
Compounds
117
293 305
Nonradiative Processes
Fluorescence
118
307
Index
315
INTRODUCTION
Molecular spectroscopy
is
electromagnetic radiation
by
molecules.
and the amount of radiation emitted or absorbed by the sample. One can often understand the nature of the molecular changes that
are responsible for the emission or absorption of the radiation.
cases,
In such
In this way, as
size,
shape,
obtained.
It will
and electronic arrangement of a molecule can be become apparent that spectroscopy offers one of the
most powerful tools for a great variety of molecularstructure studies. Only brief mention will be made of the experimental techniques used
to obtain the spectra that are discussed.
A number
of books, listed at
the end of this section, deal in part or wholly with these techniques.
practice, furthermore,
In
many commercial
There will, furthermore, be no attempt to deal in detail with the tremendous body of very useful empirical data that has been accumulated,
primarily from studies of infrared and ultraviolet spectra. References some treatments and collections of these data are given below.
Classifications of Spectroscopy
to
When
is
treated,
it is
convenient to
is
being
In this
way
the principal
is
These are
Rotational spectra
molecule
due to changes the rotational energy of the Vibrational spectra due to changes in the vibrational energy of the
in
molecule
Electronic spectra
components as has been implied by this classification. We will may result from transitions in which more than one type of molecular energy changes. Thus an absorption of energy due primarily to a change in the vibrational energy may show the effects of accompanying rotational energy changes.
electronic
see,
One can
used.
It
happens that the categories obtained in this way are similar to The instrumentation classification those based on molecular energies.
might be given
as:
and
ultraviolet spectrometer:
electronic spectra
of
by means
Raman
or ultraviolet spectrometer.
resonance
spectroscopy.
categories
The energy
result,
these spectroscopic
in
In nuclear
field is to
effect of the
magnetic
INTRODUCTION
suitable frequency can then be used to study the energySimilarly, in electronic spin resonance spectroscopy
A
and
are
Inc.,
is oriented one way or the and again the resulting energylevel separathese two orientations is studied by radiation of suitable frequency. number of recent books have appeared which provide excellent
Of particular interest electronic spin resonance spectroscopy. "Nuclear Magnetic Resonance," McGrawHill Book Company,
New
in
HighResolution
Inc.,
York, 1959, and "An Introduction to SpinSpin Splitting Nuclear Magnetic Resonance Spectra," W. A.
York, 1961, both by J. D. Roberts, and "ApplicaMagnetic Resonance Spectroscopy in Organic ChemisIn try," Pergamon Press, Inc., New York, 1959, by M. L. Jackman. view of these treatments, which are at the same level as the treatments of rotational, vibrational, and electronic spectroscopy given here, no discus
Benjamin,
New
tions of Nuclear
and
included.
must be summarized.
and magnetic
Ordinary
fields
more con
Figure
indicates the
FIG.
E = E cos2irv(tf)
and magnetic fields that are associated with polarized electromagnetic radiation which has only the xz plane component of the electric
electric
field. field,
In spectroscopy almost
all
1
attention
is
shows that
component
The
and
mag
with a velocity c. The value of the electric field along the z axis at a given time and at a given point on the z axis as a function of time can be expressed by the formula
E =E
cos 2wv (t
J
(1)
This formula,
oscillation of
it
E with
wave
respect to time
given.
With
sists of
this
waves
of varying electric
and magnetic
field
strength traveling
with the velocity of light and having a given wavelength and frequency. As can be readily verified by considering a position with some fixed value of z and asking how many cycles pass this position in the time c seconds,
the relation between the wavelength and the frequency of oscillation of
the
wave
is
"I
Although, as will be seen
later,
W
the frequencies of the radiation that
more
directly related to
it is
The corpuscular
is
His
equation
Ae
hv
(3)
INTRODUCTION
where
h,
a constant
known
X
of
10 27 ergsec, ties together the corpuscular quantity Ac, the energy of a
radiation energy packet, or quantum, with the
or X to
One
addi
which
v
is
proportional to
and
is
often used.
differs
from
by the
It is
designated as
and
is
defined as
(4)
*\
The units of
v
cm1
wave numbers.
a measure of
by the constant
The ranges
shown
in
Table
1.
While
it
may seem
unfortunate that a consistent set of units, such as the cgs wavelength unit of centimeters, is not used throughout, it is a historical fact that
much on
its
own, independits
own
con
tion,
by
v,
or
by the value
of Ae
hv.
all
the
2.
shown
in
Table
be pointed out, with regard to the entries in Table 2, that a term such as cal/mole is intended to mean calories per Avogadro's number of particles, where the "particles" may be molecules, atoms, or
quanta.
TABLE
1
Microwave
X (cm)
Infrared
Visible
Ultraviolet
300.1
0.0030.00025
X(A)
V
10 6l
10 5
3,0001,000
1000300,000 megacycles/sec
3004,000 cm"
cal/mole
erg/molecule cv
X
1
10 11
5.036
X
1
10 16
1.439
X
1
10 16
cm 1
cal/mole.
. .
.
X X X
8,067
10"
10" "
23,060 2.858
0.3499
1.
Complete Table
by
filling in all
2.
Calculate typical energies of an Avogadro's number (6.023 X of quanta in the four regions of electromagnetic radiation shown in
3.
1.
these values with the classical thermal kinetic energy 600 cal/mole per degree of freedom at room temperature and with chemical bond energies of 50 to 100 kcal/mole.
Table
of
Compare
?RT =
PRINCIPAL REFERENCES
Experimental Methods
1.
Englewood
Cliffs, N.J.,
1948.
2.
Gordy, W.,
W.
John Wiley
3.
Cliffs, N.J.,
&
New
York, 1953.
Inc.,
Englewood
Applications
1.
Bellamy, L.
Sons, Inc.,
J.:
of
&
New
2.
of Inorganic Substances,"
Reinhold
New
York, 1961.
3.
"An
&
Co.,
London, 1954.
The development
of theories of
about 1900, been closely tied to the study of their spectra. The principal aspect of these theories that must be introduced here is their statements about the energy that an atom or molecule can have. An appreciation
of the restrictions that are placed
systems
is
While
standing
is
many
usually obtained
if
some
theories are
known. In this chapter, the general nature of theoretical treatments of atomic and molecular systems will be introduced to the extent needed for the treatments of molecular systems given in later
chapters.
11.
The
restric
tions stems from Planck's studies of the radiation emitted by hot bodies.
driven to assume, as was later stated, that the oscillating atoms of a hot body cannot have any energy of oscillation but can have only the energies that are integral multiples of hv, where v is a frequency of
He was
oscillation
a proportionality constant, Planck's constant. Furthermore, radiation from such an oscillating system consists of the
and h
is
energies emitted
levels to
a lower one.
when an oscillator jumps from one of the allowed energy The unit, or quantum, of energy given out in such
is,
therefore,
hv
idea of discrete energies and the prominent role played
The
tion.
since,
by the
to be
features
Planck's
blackbody theory was, however, a preview of the developments in molecular theory and spectroscopy that were to take place in the next half
century.
His
reluctantly
proposed
ideas
of
quantum
restrictions
by analyses
by and
complexity.
In the next few years after 1900 the ideas of Planck were applied
and extended, as
heat capacity of
and the
The next major step of spectroscopic interest was the application of these ideas of quantum restrictions to atomic systems, in particular to the hydrogen atom, by Niels Bohr in 1913.
12.
the discussion here, the Bohr theory provides a clear and concrete
illustration of one of the most important quantum rules and is, therefore, worthy of study. By 1913 it was recognized, as a result of the then recent work of Thomson and of Rutherford, that an atom, in particular the hydrogen atom, consisted of a small heavy nucleus carrying the positive charge and that the electron moved, or resided, in some manner out
way
that
its
angular
electrostatics lead to allowed orbits for the electron, each allowed orbit
The
derivation,
in
brief,
is
momentum
mvr
where
orbit.
= n jjis
n =
1, 2, 3,
(1)
v its velocity,
and
the radius of
its
by the
t =
r2
^
r
(2)
or
mv 2
where
e is
(3)
Elimination of
2
i>
,
by means
of the
quantum
Eq.
(1),
is
allowed to travel as
(4)
n'
47r 2
me 2
0.529n. 2
angstrom
n =
1, 2, 3,
(5)
1
The convenient
been introduced.
A =
10
8
cm, has
Of more interest in spectroscopy are the energies of the allowed orbits. If the potential energy at infinite separation of the electron and proton is taken as zero, the potential energy at separation r is given by
Coulomb's law as
PE =  r
(6)
Addition of the kinetic energy gives, for the total energy of the electron,
the result
t
= KE + PE =
g
mu2
7
of the relation of Eq. (3)
(7)
restric
= fcivsy
w =
1>
2 3
'
<
8>
10
by writing
made
account that the electron and nucleus should be treated as rotating about the center of gravity, which is not quite at the
nucleus,
velocity.
and to include the relativistic dependence of electron mass on These details need not, however, be treated here.
angular
momentum
Further
atom is now assumed to jump from one orbit to another, say from that with n = n,\ down to that with n = ni, the Bohr theory predicts that an amount of energy Ae = e, e must be emitted. With the Planck relation Ae = hv, the Bohr theory leads to
the electron of the hydrogen
(l!
'
At
T
v
2ir
f^\n\ ~ </
l
me*/l
Wlth ni
>
,
W2
^
has the prediction
(10)
cm 1 one
2w*me /l
1\
"c'ehrltf*)
>
cm
109,677
(11)
expression,
cm
(11)
Exercise
11.
He +
ion.
The
will
principle of quantized angular momentum used by Bohr is, as be seen, a very generally applicable one in atomic and molecular
systems. A more complete statement of the principle applied to the simple Bohr hydrogen atom would recognize that not only must the total
angular
momentum
momentum
Thus
for the
if
a direction
field,
is
imposed on
the component of
angular
h/2w.
must
is
also
be quantized in units of
n = 2
orbit, for
momenby
tum
and there
field
momentum components
The
of
2(V2ir), l(h/2w),
0,
splitting of the
2 state
by the
same energy.
One says
that the n
is
has a multiplicity of 5 or
fivefold degenerate.
will
The
details of
not be developed
further here.
some further general theoretical developments which led finally to the more powerful and less ad hoc formulation of quantum restrictions than that of Bohr will be outlined.
Instead,
13.
The
Wave
Nature of Particles
with them.
particle with
He
mass
and velocity
v, i.e.,
momentum
mv, would be
given by
X
mv
if it is
(12)
For
wave associated with an electron in a Bohr orbit should form a standing wave around the nucleus, the condition that 2irr = n\ where n is an integer and 2irr is the circumference of the
is imposed. This stipulation together with de Broglie's wavelength relation leads, interestingly, to the same requirement, i.e.,
electron orbit
mvr
n(h/2w), as imposed
by Bohr.
Even more
shown
It
Germer
in
length given
by the de Broglie relation. became .clear that the Bohr condition, while
way
this wave nature of the electron. The importance of the wave nature led ultimately to a formulation of a general approach to the
illustrate this
approach by means of
It is of great
an equation given
appreciate the
described
by Erwin Schrodinger.
of Schrodinger.
value to
way
12
14.
it is
convenient
first
to
is
little
is
= ma
it
expression.
The Schrodinger
equation, like/
ma,
is
wherever
Use
we
are interested in
subject to
some potential
by the
particle.
was
in agreement with experiment. Bohr's method could not, however, be extended to more complicated systems. The Schrodinger equation
for
example, be used to solve again the hydrogenatom problem and predict the position and the energy of the electron exposed to the coulombic
potential of the nucleus.
The Schrodinger
particle
is,
under study.
The
position of the
we
can move only along one dimension, say the x coordinate, the solution
function, or eigenfunction, represented
by
\//,
will
be a function of
x.
For
^/{x).
The
is
x.
is
(If
\p is
a complex function, as
given by
^V, where
is
jugate of ^.)
13
The Schrodinger equation for a particle of mass m constrained to one dimension and subject to some potential function U(x) is
fe
8ir
m da; +
2
dy
U(x)+
e*
(13)
(The
fore,
first
term can, in
fact,
particle,
the second with the potential energy, and the sum, there
perhaps better at
first
merely to
much
ma.)
Solution of a particular problem requires values of
m and an expresfunction
ip
The
e,
that
Such a
are the allowed energies of the system that are being sought.
The square
and the expression (The hydrogenatom prob/r to be put in as the potential function. lem is, however, three dimensional.) Solution of the problem would give the allowed energies, which turn out to be identical with those obtained by Bohr. The ^ 2 function would give the probability of the electron being at various positions, and the probability that is found is related to, but not identical with, the Bohr orbits. Before the equation is illustrated by a simple, but important, example, it is necessary to state some of the limitations that are imposed on the function f. Briefly, the function ^, to be an acceptable solution, must be "well behaved." It must not, for example, go to infinity or be double valued. In the first case one would deduce from the infinite value 2 an infinite probability of the particle being at a given position; of while in the second case one would have two different probabilities at the same position. Neither of these would be physically reasonable. Further restrictions are that the function must be continuous and that discontinuities in the slope can occur only at points where the potential energy goes to infinity. One understands these restrictions from the fact that the equation involves the second derivative of and that this would go to infinity at a discontinuity in the slope. The equation and its application are more understandable when
require the value of
for the electron to be used
\f/
\[/
'
U
15.
move
This problem implies a potentialenergy function that has some value, which can conveniently be taken as zero, between x = and x = a, and is
is
a.
An
is
subject to a potential
which for some purposes can be so represented. Of more spectroscopic interest, as will be shown in Chap. 11, is the fact that the doublebonding, or t, electrons of a conjugated system of double bonds in a molecule behave approximately as though the potential which they experience is
such a simple squarewell function.
In the region
<
<
is
U(x)
0,
dV
dx i
potential
is
infinitely high,
and there
is
and prevent a discontinuity and a must be such that it equals zero at x = and at x = a. Functions which solve the differential equation and also satisfy these boundary conditions can be seen by inspection to be
well behaved,
in
4/,
To be
in the region
between
i = A
and
x
sin
where n
factor:
1, 2, 3,
(15)
is
some constant
The
n.
and at
the
satisfies
.,
Lett side
h2
7r OT
2
(
I
nV \ jA
2
.
nirx
sin
n 2h 2
8ma 2
Right side
sin
J
(17)
15
The
left
and
^ =
sin
if
m3A J
8ma s
n =
1,2,
3,
(18)
No
[The value n
Eq. (14) but gives a wave function that is everywhere zero. This leads to a zero probability of a particle being anywhere in the box and is therefore unacceptable.]
The allowed
energies
t,
in
Fig. 11, are seen to be quantized as a result of the quite natural intro
duction of the integers in the solutions of the Schrodinger equation. A and molecular problems.
The quantum phenomena, which were so arbitrarily introduced in the Bohr theory, are seen to result much more naturally in Schrodinger'
approach,
FIG. )]
Energies,
wove
functions,
and probability
problem.
e4
16(A /8
ma
2
)
t3
= 9(r/8ma)
= 4<ft J /8ma*)
16
The
ii
sin
^
are
= A*
sin 2
(19)
many
of the characteristics of
more
difficult
systems.
One
cor
number.
A number
In these cases,
it will be have the solution functions and allowed energies stated with
out derivation.
As an
r electrons of a These electrons are apparently delocalized and are relatively free to move throughout the length of the molecule. One can therefore approximate such a system by representing the molecule as a
conjugated system.
onedimensional region of uniform potential bounded by regions of
infinitely high potential.
The allowed
.
energies of the
ir
electrons, ignor
by the previous
approxima
= n 2 2/8ma 2
/i
To apply
this squarewell
it
quantum numbers the same. Since the spin of an quantum number of +^ or two electrons can be accommodated in a state represented by a single value of n. The occupancy of the energy levels by the six k electrons of hexatriene is represented in Fig. 12. The success of this simplification of the factors affecting t electrons in conjugated systems is judged by
cule
have
all their
J,
the comparison of the energy calculated for the promotion of one of the
highest energy electron pair to the next higher energy state with the
energy of the radiation quanta absorbed in an electronic spectral study. The agreement, as Exercise 12 illustrates, is remarkably good.
Calculate the wavelength of the radiation that will be Exercise 12. absorbed in the lowest energy irelectron transition of hexatriene according The length of the molecule can be taken as to the square well model. with A. Compare the observed value of 2,580 A. about 7.3
16.
Normalization of
It is
Wave
Functions
frequently convenient,
when
wave function f
is
obtained for a
shows that there is a value of unity for the total probability of the particle being found somewhere in space. In terms of a onedimensional problem this implies that
particle, to
arrange
it
so this function
/:
if/*
dx
is
(20)
r dx
(21)
is
said to be
FIG. 12
electrons of
hexatriene.
occurs
when
absorbed.
18
such that
o /.
= A*sm*dx a
(22)
The
an
if
m is
integer,
sin
my dy =
t/2) to give
o /o
rin*^fa = o, Z
(23)
or
A =
^
"i"
(24)
Va
Sm
(25)
and usually
tion
are, normalized.
case,
if
on a wave function
\[/
is
+ ." /_ i*dr
or, if
(26)
+ = /_ " ^** dT
17.
<
2? )
Orthogonality
general property of
wave
functions,
i.e.,
that of orthogonality, a
Two
wave functions
\f/i
and
^/
where
and
/+
Mm dr
19
more
generally,
+ ." +*+ dT /_
if
I
(28)
and
This property
It can, however,
be readily
It is necessary to
show that
sin
o JC
sin
ax
=
= rx/a
converts the
(^9)
for
of
m.
left side
Eq. (29) to
/
"
sin ly sin
my
dy
where,
this
are integers.
The
integral in
terms by
sin ly
jp (e"
e"")
and
sin
my =
^. (e
imy
<r im )
(30)
and performing the integration on the exponential form of the integral. In this way one obtains zero for the integral and verifies the orthogonality
statement of Eq.
(29).
an example of the general orthogonality result that is applicaSome addible to the wave functions for states with different energies. tional features must be considered when there are several states, i.e.,
This
is
wave
summary
of this
4> t
statement that
if
and the previous section can be given by the and 4*m are normalized, real, wave functions cor
/+.,,
These properties,
for
a*
/o
it will
number
of spectroscopic problems.
20
18.
Symmetry Properties of
Wave
Functions
is
general property of
is
important in
many
form when, as is often the case, the potentialertergy function is a symmetric one. The potential of the particleinabox problem, for example, is symmetric about the point x = a/ in Fig. 1T. It is apparent from the plots of the wave functions shown in
spectroscopic problems
Fig. 11 that those with
metric about the midpoint of the well while those with odd values of
are symmetric.
Such symmetry properties are characteristic of wave functions that arise from a problem with a symmetric potential function. Generally, it is more satisfactory to use the center of symmetry, such
as the midpoint of the square well, as the origin of the coordinate system.
If this is
cosines as
done in the squarewell case, the solution functions are sines and shown in Fig. 13. It is then possible to investigate the sym
metry properties
when
is
done for
FIG.
1
wave functions by investigating what happens in a. particular wave function. When this is the functions shown in Fig. 13, one sees mathematically that
of the
replaced by
3
functions.
(The
wave
function!
Wave
function 4'
Symmetry nature
of
Odd
function, antisymmetric
i =_**
#2 =
sin
*M
Odd
function, antisymmetric
* ?
a/2
+'2
+y
21
For n odd
Hv) = Hy)
For n even
(32)
My) = Mv)
Again one sees that for odd values of n metric, function; while for even values
antisymmetric, function.
*l9.
the. function is
of
quantummechanical
will
results of
properties.
particle for
from solution
of
The method
be introduced.
momentum, and
operator.
If
what
is
called
an
denoted by g and the operator for this function by G, then operation on the wave function of the system by
one of these variables
will give, in
some
i.e.,
G+ = g+
Only a few functions and
these are listed in Table 11.
their operators will be encountered,
(33)
and
The operator
is,
used to
gf.
'
The
kinetic
for onedimensional
axis,
Tx
= ~ h d &r^ te
2
2
(34)
The
Since ^
= A
sin nrrx/a,
by Tx
gives
87r
m (^Xt)'*
sin
?
(35)
wVa
ir
w*
22
Here operation on ^ by
Tx
gives a quantity
nW/Sma*
n 2 /i 2 /8ma 2
times ^.
Since
This
energy
was taken as zero, agrees with that obtained previously. One further feature of the nature of these operators must be pointed Sometimes an operator acts on ^ and does not lead to a number, out.
such as
re
2
/i
/8mo 2
wave
function.
momentum
_ /
/2
Sm
titx\
T)
h
2Vi
[2
/rar\
nwx
C S
VH \T)
IT
r,
(36)
TABLE 11 Some Quantummechanical Operators (In terms of cartesian coordinates x, y, z and polar coordinates
Variable
Position
6,
<f>)
Operator
x v
z
x y
z
Linear
momentum:
h
2jr
dx
h_d_
Pv
P.
2fridZ
2vidy
h
a
Angular momentum:
M M
v "
VriVaz 2xiV
h /
a
\y
I
a\ or
ay/
}
sin
6
x
a
cot S cos
d>
a\
I
2iri
ae
34,/
h / a \z
h /
a\
J
or
ax
at)
d>
cos a
cot
fl
sin
d>
a\
2irt\
ae
a<t>J
h
'
a\
/)
2irt \a<t>/
M =
M I + Ml + Ml
j^_
2
r_i_
a_
/
".
4t Lsin e ae
h*
v
(
m
i
a\
ae)
a'
l_
sin* e
aa 1
a* 2 J
Kinetic energy:
a2 \
i^vl+vl+vl)
Potential energy:
V{x,y,z)
^Kw+W+6*)
V(.x,y,z)
23
is
is
Rather
it
has various
of the
+"
f*G+dT
(37)
+ y*idr f_
For normalized functions the denominator is of course equal to unity. For normalized, real functions, the average value of a variable is,
therefore,
"lKtydr
(38)
this relation as
jo
ia
2
W
fa
/
.
Sm
mcx\ h
rmx
a
/2
(nir\
IT) 2S V
cos
j
U T
CS
nvx
dX
nh = i;
nwx
a
["
.
sin
ax
Jo
_ nh
ia?
/ a \ \2mr)
titxI"
_
a Jo
(39)
=
The
result of
classical picture of the
an average momentum of zero reflects the fact that the motion of the particle would ascribe both positive and negative values to the momentum since the particle would move in
either direction.
Exercise 13.
n =
Obtain the average position of a particle in a box in the method of Eq. (38).
made
in a
number
of
will in fact
be occupied
by the molecules of the sample. In the particleinabox example the question that would have to be asked is: If some large number (frequently it is convenient to consider an Avogadro's number 6 X 10 23 ) of
particles are placed in such a potential well,
how many
will
behave
according to the n
wave
function,
i.e.,
occupy the n
1 level;
how
24
many
the
n = 2
level;
and
so forth?
was made.)
state with
The answer
to such questions
is
of particles
N, occupying a
energy n will be related to the number N, occupying some state with energy ts which is lower than a, by the relation
,
^f
e(..,mr
40 )
where k is Boltzmann's constant, 1.380 X 1016 erg/deg molecule. If it is more convenient to measure the energies of the states in calories per
mole, the appropriate expression
is
^!
(E E,)IRT
t
(41)
where R, equal to Nk, is 1.987 cal/mole deg. Most often one is interested in the number of molecules in a state with an energy t compared to the number in the lowest energy state to. The appropriate form of the Boltzmann distribution is then
t
Ni
JVoe<** r
(42)
Sometimes, as was mentioned in Sec. 12, there are several states The population of the energy level is then cor
Thus
is
if
gt is
the
number
of states
with energy
and as
e
is
energy
Ni=.giNoe^^ ltT
[Note that the number in each state at energy
e,
(43)
is still
( " , )/ * T
There
are,
a.]
THE VIBRATIONAL
ENERGIES OF A DIATOMIC MOLECULE
The
now be
and a pair
Then the corresponding problem with molecularsized units and quantum mechanics will be studied. The energy levels deduced in these calculations will then be
levels indicated
We will see that changes in the vibrational energy of the simple systems dealt with here lead, in spectroscopic studies, to absorption of
radiation in the infrared spectral region.
well be
show
The
rather
interesting, systems.
Thus, Chap. 4 will deal with the transition process that takes a molecule from one energy level to another, and Chap. 6 will recognize that gasphase molecules engage in simultaneous rotation and vibration and that it must be shown to what
extent these motions can be treated separately.
It
seems desirable,
25
26
be apparent from the next few sections that an understanding i.e., ordinarysized, particles which can
be described by classical mechanics is very helpful when the quantummechanical behavior of molecules is encountered. The simplest classical
vibrational problem
is
is
The
effect of gravity
here ignored.
is
asked
is:
What
m undergo?
among other things, on many springs are such that if
it
The answer
the spring.
It is
clearly depends,
found that
its
equilibrium position,
experiences a restor
FIG. 21
in
by
(a)
a diatomic
is
molecule and
in
a polyatomic molecule.
a molecule, the more ways the molecule can vibrate and the more complex
Wave numbers
4,000 5,0001 3,000
in
cm 1
900
1
2,000
800
1
700
1
62
100
80
60
x V
<
40
20 COin CCI 4
n
100
(a)
ft
8
in
9
microns
10
16
Wavelength
(b)
A DIATOMIC MOLECULE
is
27
position.
law.
A spring which behaves in this manner For such behavior one can write
<*
said to
obey Hooke's
/
or
(1)
= kx
x,
(2)
where
is
the displacement coordinate, f is the force which the spring imposes on the particle, and A; is a proportionality constant called the force constant.
It
k,
which
will also
appear
position.
in
molecular
i.e., it
The minus
Eq.
FIG. 22
The
displacement
is
from
the
in
equilibrium position
(a)
measured
in (b)
of the spring.
28
directed in the
opposite direction.
Before proceeding to the problem of the nature of the vibrations, it is important to point out that Hooke's law implies that the potential energy
of the particle increases parabolically as the particle
is /, PI)iied
and
this
work
is
stored as
Thus
(3)
dU = /,pP
It is
ii.d
dx
to deal with the force / that the spring exerts
more convenient
particle and, since it is this force that the applied force acts against,
on the one
has /
/.ppii.d
and
dU =
or
(/) dx
(4)
dU
dx
This
is
_
J
energy.
= kx,
the potential
energy derivative
is
dU j =
dx
or
kx
(5)
dU = kxdx
If
is
U = Px*
This potential function is illustrated in Fig. 22. The statement of Eq. (6) is therefore equivalent to that of Eq.
(6)
(2),
be encountered again
.
later,
The force
is
Sometimes a problem is more conveniently set up in terms of the point than position of the particle measured from some other reference
OF A DIATOMIC MOLECULE
If,
29
= k(l 
k)
and
U=
l,)*
(7)
now be
set up.
Newton's /
= ma
equation to
kx =
mji
d %x
or
kx = mx
to start with statements
particle.
%
(8)
One then
writes
.
Kinetic energy
Potential
An
= ma
that of Lagrange
dT
ax
,.
= mx
and
d (dT\ = mx dt\Tx)
mx
as set
kx
or
kx = mx
of the
(11)
up by Newton's f = ma relation, is obtained. The differential equation, Eq. (11), has a solution
x
form
(12)
= A
cos (2wvt
<p)
The
and
by
= 4tVA
if
*>)
(13)
differential equation.
When
this is
4f7r 2 v 2
m = k
(14)
or
1
Ik
2t
\m
30
This equation
is
It
shows that a
held by particle with mass according to Eq. (12) with the frequency v given by Eq. (14). Only this frequency is allowed. The energy with which the particle vibrates can
maximum
displacement,
i.e.,
the amplitude
of the vibration.
The quantummechanical
from
will
classical
to molecular systems.
Consider
The
particles will,
is
FIG. 23
The shape of the potential energybond length curve for a diatomic molecule.
is
defined as
r,.
A DIATOMIC MOLECULE
31
and
from
initial positions in
if
mass wii and which the particles were separated by their Hooke's law is assumed for the spring, the
T =
and
wi2X?) "
(15)
U =
Xl
Although one could solve the problem by writing/ = ma for each particle, the use of Lagrange's equation, which will be important in later work,
will
be illustrated here.
i,
equation as
d/dT\,dU
,,,..
is
Two methods
which are presented here because they introduce methods that encountered in molecular vibrational problems, can be used.
a.
be
Direct Solution.
With
= ma
miXi
fc(.r 2
if
x\)
=
(17)
and
m X2 +
2
k(xi
X\)
=0
problem
X\
exist.
We
A\
cos COS
(2irvt
<p)
'
and
Xi
(18)
= A2
(2irvt
<p)
may
and
</>)
if a vibrasystem and
2.
= 4x
2
i'
Ai cos
+ +
2
and
Xz
(19)
= 4jr
v 2 A.2
COS {2wvt
<p)
on rearranging,
(20)
(4ir 2 v 2
m +
l
k)A t
 kA =
kAi
+ (
45rVw 2
k)A 2
32
This
is
A 2 from these two equations to get a relation most conveniently done by recalling that for such linear
nontrivial solutions for the A's will exist only if the
is zero.
homogeneous equations
That
is,
(47rVmi
k)
(
k
4jr
m +
2
k)
(21)
4rVfc(mi
+m +
t)
k1
fc
(22)
(23)
and
2~ \/~ 2t \h
where
= ^ wi2 mi + ^
_^_
(24)
The quantity p which is introduced here will be frequently encountered and is given the name the reduced mass. There are, therefore, two natural
frequencies for the system, one of the frequencies being zero.
A\ and A 2
is
found.
after rearranging,
Ai
= A
(25)
and, therefore, Xi
sists of
x2
to
con
direction.
The
Ay = A,
and
Xi
my
(26)
TO 2
Xi
If
my
= At. and
xi
= z2
The
motion corresponding to
1/2* s/k/y.
A DIATOMIC MOLECULE
33
equal
be
have the frequency v = 1/2t s/k/ii. It should be recognized from Eq. (26) that if the masses of the two particles are not equal, the lighter one will move with a greater amplitude than the heavier one. Thus if Wi is less than w 2 Eq. (26) shows that the amplitude of particle 1 will be correspondingly greater than that of
one of vibration and
,
particle 2.
Exercise 21.
of Eq. (21)
b.
Obtain the relation between A and A 2 for the two roots by comparing the appropriate minors of the determinant.
x
The
mode and
up in terms of coordinates which are especially suited to describe these motions. Thus, rather than displacements xi and x 2 one could choose to use the coordinates
,
Q.
Xi
Xl
(27)
X = m&i + mzXz mi + m
2
measure of the displacement of the distance between the from the original equilibrium value, and X is a measure of the displacement of the center of mass of the system. In terms of these coordinates one can immediately write down the potential energy as
q is a
Now
particles
U=
The
4*(zi
xt)*
is
ikq*
(28)
kinetic energy
coordinates.
Thus
T =
i(m,*;
+ m z)
2
This expression must be converted to one involving q and X. From Eqs. (27) one obtains by rearrangement, or by forming the
inverse transformation,
Xi
= A = A
q
(29)
and
Xi
+ mi + m
^,
,30)
34
to the coordinate
q,
then gives
+ +
kq
=
(31)
or
nq
kq
particle.
This can be recognized as identical to Eq. (11) for the vibration of a single Only a change in notation from m to n and x to q has occurred.
as that for Eq. (11),
The solution to Eq. (31) is, therefore, the same we can write down the solution as
q
and
= A
cos (2wvt
<p)
(32)
and
'
*4
for
(33)
term
mi)X =
X=
A
solution which
is
(34)
is
X= A
with
v
cos (2rvt
<p)
0.
t
Alternatively
one
const
system.
The advantage
translational
and vibrational modes initially is that one ends up with one equation which determines the vibrational motion and another which determines the translational motion. Previously, two simultaneous equations were obtained, and these had to be solved to extract the desired information on the vibrational motion. For problems of much complexity it is of great value to eliminate the translational and rotational motions before the vibrational problem is developed.
Exercise 22.
x's in
By finding the inverse of the transformation matrix for the terms of q and X, obtain the expressions of Eq. (29).
23.
A preliminary to
OF A DIATOMIC MOLECULE
35
the variation of the potential energy with the position of the atoms. More particularly, for a diatomic molecule, one asks about the change in
potential energy of the molecule as a function of the distortion of the
of the molecule
bond
from
its
equilibrium distance.
2 , it
energy of the molecule as a function of internuclear distance from the The interactions between the bonding electrons and the atomic nuclei. general shape of the potentialenergy versus bondlength curve can, however,
far
be sketched. One knows, for example, that if a bond is stretched enough it will break, i.e., a molecule can be dissociated, and that bonds
that will
Fig. 23.
by the relative and more exact ones be developed, lead to a potential curve of the form shown in
is
Such qualitative
Although no exact mathematical expression for the potential energy all molecules is known, a simple and often convenient one that yields curves of the shape of that in Fig. 23 has been given by P. M.
curves of
Morse.
U(q)
He
e<") 2
(35)
where, as before, q measures the distortion of the bond from its equilibrium length; D e is the dissociation energy measured from the equilibrium position,
for
i.e., from the minimum of the curve; and /3 is a constant any given molecule and can be said to determine the narrowness, or The Morse curve with the values of curvature, of the potential well. D e and j3 that are appropriate to HC1 is shown in Fig. 24.
Exercise 23.
The value
of
/?
in the
0_,
W^
1
.
1 for H 2 for which <b e = 4,395 cm and D e = 38,310 cmDetermine = using 5.2 k X 10 6 dyne/cm, and Morse Plot the harmonic oscillator, (The quantity we curves for H 2 as has been done for HC1 in Fig. 23. is related to the vibrational level spacing as will be shown in Sec. 26.)
would be to substitute the Morse function into the Schrodinger equation and, in much the same way as was done for the squarewell
energies
problem, to look for functions that solve the resulting differential equaThe pattern of allowed energies, known in terms of e and /3, tion.
36
Some mathe
matical difficulties arise in this procedure, and a simpler and more fruitful
procedure
is
followed.
It will
equilibrium length.
In a study of
we
are,
therefore, particularly
an expression for the potential energy near the minimum This suggests that a suitable expression
by a
series
minimum.
If q is
equilibrium
=
q*
gives
U(q)
!7_,
(dU\
\dq),<>
9
/dHJ\
2\dq*) Q=
,
(36)
or q = 0, sets t/ g _o equal to zero. re Furthermore, at q the potential energy is a minimum, and therefore (dU/dq) g =o must be zero. If only the next higher term in the expansion is
The usual
choice of
U=
at r
FIG. 24
The harmonic
oscillator
(dashed
line)
and Morse
(solid line)
potentialenergy
functions for
HO.
40,000
30,000
E u c
i
e
3
20,000
10.000
V=
134,000(p
re
y\
OF A DIATOMIC MOLECULE
37
retained,
we have
This result should be recognized, by comparison with Eq. (6), as identical to that which would have been obtained if it had been assumed that a chemical bond behaves as a spring following Hooke's law. (For a true
is
equal to k at
all
values of
q; i.e.,
is
For a chemical bond the curve can be said to approximate a parabola only near the minimum. The force constant is then the value of d 2 U/dq 2 near the minimum.) Figure 24 shows the parabola that fits
the Morse curve for
HC1 near
the
minimum.
is
When
oscillator.
24.
The
by method
b in Sec. 22
showed that the vibrational equation that arises for the vibration of the
twoparticle system
form to that for a single vibrating particle. It is only necessary to replace m by /i and x, the displacement of the single particle from its equilibrium position, by q = Xi X\, the distortion of the distance between the two particles from the equilibrium bond length. The same situation is true in the quantummechanical problem. The Schrodinger equation for a single atom of mass m subject
is
identical in
to a potential of
U=
%kx*
is
while that for the vibrations of a diatomic molecule with reduced mass
ju
is,
correspondingly,
?& + (I *A+* = ^ ^
8* 2n dq 2
fcQ;2
V2
(39)
The deduction
quantum mechanics.
The
procedure should be recognized to be essentially that followed in the simpler squarewell problem.
38
would be expected from the similar squarewell probe and that these functions, and the values of t, are characterized by a quantum number. Thus, there are again certain allowed states, and each of these states has
lem, that solution functions exist for certain values of
a specified energy.
represented by
v.
The
It
is
usually
The
by the expression
(' +
5)s>
where
0, 1, 2,
(40)
These allowed energies are shown, along with the potentialenergy function, in Fig. 25. The appearance in Eq. (40) of the same quantities as
in the classical calculation of
This
=3
i>
=2
=l
FIG. 25
The harmonicoscillator
wave
v
functions
A DIATOMIC MOLECULE
39
problem
is
.(
where w
i)fo*
is
41 )
1/2t y/k/p
(In to Eq. (14), the system would vibrate if it behaved classically. what follows, to will be used for a molecular vibrational property and v
will
The form
in Fig. 25.
is
also
shown
Although little will be done with the solution wave functions themselves, it can be mentioned that each involves a set of series terms known as a Hermite polynomial. If one introduces a as
a
27r
^
h
v v
(42)
N el<>'H
(V*q)
where
0, 1, 2,
v.
(43)
and
v is
The normalizing
factor
2Vis
^ = (^^\ V2V.VV
"
(44)
it
will
shown
it
in Fig. 25.
polynomials
first
may
For those unfamiliar with the Hermite be informative, however, to write down a few of the
solution functions.
*o
=
=
(i)'
/
e iaq'
ft
4>i
= y= (Y =
1)e_i "'
(45)
** fa
Vi ()*
(f\'
{2aiq3
~ 
Zaiq)e
~ iaq '
= ^=
(4a 2 g 4
12ag 2
3)e*"
The
now be
25.
40
25. Vibrational
The previous
tion that
is
levels of
vibrating molecule form a pattern of equally spaced levels with a separarelated to the molecular properties
= ^,. =
A^
(46)
The
be expected to arise from such an if one also knows what transitions can occur with the absorption or emission of radiation and what energy
spectral transitions that are to
temperature of the experiment. Although the interaction of molecules with radiation will be dealt with in Chap. 4, some of the results that will be obtained can be mentioned here.
First of all, it will be shown that a vibrating molecule cannot interact with electromagnetic radiation unless a vibrating, or
oscillating, dipole
litatively,
moment accompanies the molecular vibration. Quaone can picture an oscillating dipole as coupling with the
energy can be exchanged between the
This stipulation that the vibration be accompanied by a dipolemoment change implies that all homonuclear diatomic molecules, which necessarily have zero dipole moment for all
bond
and
will exhibit
no
On
moment
and, generally,
moment
will
The
be
generally accompanied
can interact can thereby change their vibrational state to one of higher energy. They can, also, emit radiation energy and thereby change their vibrational state to one of lower energy.
by an oscillating dipole moment. Such molecules with radiation and can absorb energy of the radiation and
4,
One further transition restriction, which will be discussed in Chap. must be mentioned. Even for those molecules that have an oscillating
dipole
ble
moment
there
is
is
rigorously applica
Av
= 1
(47)
41
This restriction is an example of a selection rule. For absorption experiments, which are those most commonly performed, the applicable part of the selection rule is, of course, An = +1.
Now that the allowed transitions have been stated, it is only necessary to decide in which state, or states, the molecules are likely to be found at the beginning of an experiment. It will be shown that the
energy spacing between vibrational energy levels is typically of the order 13 erg/molecule or 3000 cal/mole. With Boltzmann's disof 2 X 10 tribution one can calculate the number of molecules in the.v = 1 state
in the v
state at
25C as
/)
2X10 1S /298(l.S8X10 1 )
=
Thus,
less
0.008
1
(48)
than
state,
and
It follows
The
selection rule
and population statements allow the vertical drawn to indicate the expected spectral vibrational
molecule.
found experimentally that such molecules do lead to the absorption of radiation quanta in the infrared spectral region and that this absorption can be attributed to the vibrational transition. Thus, HC1
It is
2,890
8.67
cm"
or
cycles/sec
is
X
hv
10
10
(2,890)
10
13
The energy
Ae
of the
= =
v
6.62 5.74
X X
10 13 )
.
(49)
It is this
the
=
Ae =
and
h
1 levels, i.e.,
to
lie
(50)
We
1.627
Wei
10 24 g
42
one obtains
k
4.84
10 6 dynes/cm
(51)
In this way it is seen that the spectral absorption is understood terms of a molecularenergylevel pattern and that new quantitative information about the molecule is gained.
in
The frequencies of radiation absorbed by some diatomic molecules and the deduced force constants are shown in Table 21. One should
recall that the force constant
measures the
stiffness of the
bond and
should see that the force constants of Table 21 are to some extent understandable in terms of qualitative ideas about these chemical bonds.
It should be mentioned finally that it is not customary to convert from radiation frequency to quantum energies in comparing spectral
It is
more convenient
i.e.,
to use
Ae
hv,
TABLE
21
Transitions v
to v
stants Calculated
Raman
Molecule
p(cm _ ')
4,159.2 2,990.3 3,958.4 2,885.6 2,559.3 2,230.0 2,143.3 1,876.0 892 556.9 321 213.4 1,556.3 2,330.7 246.3 157.8 378 278
k (dynes/cm)
H D HF
2 2
HC1
HBr
HI
CO
NO
F,
CI*
Br*
I*
o.
lis
Nas
NaCl KC1
5.2 5.3 8.8 4.8 3.8 2.9 18.7 15.5 4.5 3.2 2.4 1.7 11.4 22.6 1.3 1.7 1.2
.8
10 5
OF A DIATOMIC MOLECULE
43
levels of the
harmonic
oscillator
can be written as
( +
<v
s)s^
2) 2^
ergs
(52)
J
cycles/sec
(53)
The symbol
are written as v
will
cm1
expressed in
cm1
of radiation that
these expressions
one can compare the energy separation between two levels directly with
the
wave number
between these
Exercise 24.
levels;
v for
the radiation.
compared
to the
Calculate the numbers of molecules in the v = 1 state number in the v = state at 25 C C for Br 2 which has the
,
cm 1 and
,
for H2,
cm 1
26.
oscillator expression
U=
\kq*
is
only an approx
imate representation of the correct potentialenergy function shows up in the presence of weak spectral absorption corresponding to Av = +2,
+3,
in violation of the Av
= +1
= +1,
selection rule,
is
and
in the fact
2, 3,
.
.
not exactly
absorption.
The
One
This expression for the potential can be used in the Schrodinger equation
to deduce the energy levels of the allowed states of the
oscillator.
anharmonic
tion,
The solution is obtained by an approximation, or perturbamethod and leads to an energylevel expression that can be written
as
.
.(
+ *) 
^J.
(v
+ i)
(56)
44
Here
fc 8
(d 2 U/dq 2 ) q o.
levels,
This quantity w e
is,
if the potential curve were a parabola with the curvature that the actual curve has at the minimum, or equilibrium, position. The coefficient oieXe of the squared
energy
expressed in
cm1
quantumnumber term
always
is
known
It is
With the minus sign than the principal term > e written explicitly in Eq. (56) it is found that w e x e is always a positive The energylevel expression of Eq. (56) shows, therefore, that quantity. the separation between successive vibrational levels is not constant but
much
less
v,
as
shown
in Fig. 26.
It should be recognized that the broadening out of the potential curve, shown in Figs. 23 and 24, as a bond stretches, confines the
FIG. 26
Pattern (a)
is
based on the
transition.
harmonicoscillator
Pattern (b)
is
14,000
12,000
10,000
<
8,000
6,000
4,000 
2,000
Harmonic
(a)
Anharmonic
(b)
OF A DIATOMIC MOLECULE
45
vibrating particles less closely than would a parabolic curve. Such loosening of the restrictions on the motion of particles always leads to
closely spaced allowed energy levels.
more
intro
duces, therefore,
levels, as
If
v
shown
2, v
3,
and
so forth,
i.e., transitions from one can check the success of the and determine the constants o>, and
Table 22 shows the data obtained for the fundamental and first These data can be compared with those derived from Eq. (56) for the energies of the transitions from v = to v = v; i.e.,
four overtones of HC1.
i(v)
e(0)
ii e (v)
WeX^iv
1)
(57)
One
finds, for
a>
2,988.90
cm1 and
fit
u^x e
51.60
cm1
One notices that is considerably larger than the quantity (1) which would have been identified with the coefficient of the (v f ^) term in the expression based on a harmonic potential. It follows that the force constants calculated from these two quantities will be different.
i(0)
The
distinction
is
that
&>
is
= ^ level
of the
would
be.
The
v
energy of the
potential curve
u.
1 levels as a measure of the curvature and therefore gets a lower value. Thus for HC1 v
and
2,988.90
cm
K =
5.1574
10 6 dynes/cm
Comparison
(v
TABLE 22
lator
of the Observed Frequencies with Those Calculated from the Harmonic Oscil
o= 2,988.90(v)
51.60v(v
1)
Soto
cm
Av
Description
fobs
cm
'
Harmonic
oscillator
Anharmonic
oscillator
0>
Fundamental
First overtone
0>2 03
04
05
(2,885.9)
46
while
(1)
of
i(0)
Jj e
2,885.90
cm
fc
4.806
10 6 dynes/cm
is,
The use
of ways,
in
a number not
more
on the overis
tone frequencies.
this information
always available.
Exercise 25.
stretching vibration of
The fundamental and overtone frequencies of the CH CHC1 3 are reported by Herzberg to be at 3,019,
and
16,300. cm'.
What
value of u e
can be deduced?
PRINCIPAL REFERENCE
1.
3,
D. Van Nostrand
Company,
THE ROTATIONAL
it
energy of simple molecules can lead to absorption, or emission, of radiation in the infrared spectral region
ness of the
It is
now
natural to ask
also quantized,
whether
The nature of the rotational energies of molecules can be introduced by a consideration of the particularly simple systems of linear molecules.
Although diatomic molecules provide most
molecules, the theory that
is is
of the
examples of linear
first
developed
is
polyatomic molecules.
classical
It
the
in behavior that
is
of molecular dimensions
restrictions
will
become important.
No
attempt
vibration.
The
by themselves.
is
known
47
48
Such a treatment
is
31.
any system is most conveniently treated in terms and the moment of inertia /. of the angular velocity It will be recalled that a> is defined as the number of radians of angle swept out in unit time by the rotating system. For a particle moving with a linear velocity v a distance r from the center of gravity, the revolutions per unit time, usually a second, are given by v/2vr and the angular
The
rotation of
<*>
velocity
by
2
'(^H
number
of revolutions per unit time,
i.e.,
(i)
the dis
tance traveled per unit time divided by the circumference of the particle
path,
is
v/2vr or <a/2v.
of inertia of a
The moment
I
system
is
defined as
=
n
Y,
mr
'
(2)
where
out by
is
the system.
first
For any particular system, the value of / can be worked and then applying Eq. (2). For a diatomic molecule, for instance, the masses and distances of
FIG. 31
C.G.
mi
OF
LINEAR MOLECULES
49
+r = m n = mi + m r
2
2
:
r,
to the relations
and
r2
(3)
mi mi
+
r
r
wi2
(2), for
the
moment
of inertia
now
gives
.
_ =
mfm 2
(nil
+m
2
2 2)
(m t
m +m
main\ y m\
2)
r2
mim 2
mi
iur
2
+m
j
r2
2
=
where
m
n,
(4)
is
 m7 +^r 2
kinetic energy of a system of
wtim 2
()
The
given by
moving macroscopic
particles
is
^m,y?.
If
velocity
of the system.
more conveniently treated in terms of the angular One then can write the kinetic energy T as
m,coV? =
t
WX
i
"W?
(6)
= i/"
Equation (6) shows that a system of particles that obeys classical mechanics has a kinetic energy that is dependent on the moment of inertia of the system and on the angular velocity. No restriction, furthermore, is placed on the angular velocity with which the system can rotate. It can now be expected that when the same problem is treated
for a molecular
will appear.
Exercise 31.
Calculate the
linear
moment
of inertia of (a)
DC1 36
2
all of
N 0, which
(b)
and has
NN and N
bond lengths
of 1.126
and
1.191 A, respectively.
50
32.
Although a complete quantummechanical description, i.e., the wave functions and energies of the allowed states, can be obtained by
solving the Schrodinger equation for a rotating linear system,
first,
it is,
at
more informative
to see
what
result
is
momentum
of a rotating
system
is
Vi/r i} is
momentum
0, 1, 2,
. .
Iw
= j
with/ =
(8)
where the quantum number, following customary notation, has been designated by J. This stipulation leads to the allowed rotational energies
of
'Si*
The
correct result, obtained, for example,
is
(9)
by
dinger equation,
ej
= ^jJ(J + D
The
is
if
rather than
in early
quantummechanical treatments.
term, \/J(J
1)
^>
OF
LINEAR MOLECULES
51
tummechanical result
of Eq. (10),
obtained.
by application
out here.
Any
such a derivation.
of Fig. 32.
The problem
consists of setting
up the Schrodinger
and the
For a
The wave
now
can be mentioned, however, that they are identical to the angular part of the solutions for the behavior of the electron of the
concern us.
It
hydrogen atom. Thus for J = 0, the rotational wave function ^j_ has the same form as the angular part of an s orbital wave function. For J = 1, the wave function is the same as that for the px py and pz
,
orbitals,
and so
forth.
For spectroscopic work, the expression for the energies of the rotaby the quantum restrictions is of prime importance.
These allowed energies, as given by Eq. (10), are shown schematically in Fig. 33. Again it is more convenient to express these energies in
wavenumber
we have
the expression
 = sAc
The group
^ +i
>
cm1
is
(11)
of terms h/2nr i Ic
sufficiently frequently
encountered in
FIG. 32
Polar coordinates.
52
B =
h Sx^/c
em~
is
.
(12)
The used to emphasize the units of cm 1 molecule can now be written as allowed rotational energies of a linear
Again the barred symbol
lj
= BJ(J
1)
cm
(13)
FIG. 33
The degeneracy, or
multiplicity, of
if
appear
an
electric field
were applied
Allowed
rotational
2/
were removed
(schematic)
Multiplicity
,= J&/t7 +
1J
energies
30E
20B
12JJ
6B
2B OB
OF
LINEAR MOLECULES
53
Populations
The next
tional states
Now
eral,
atom treated
number
energy.
This can most easily be seen from the condition that the comIt follows, as Fig. 33 indicates, that
ponent of the angular momentum in a direction imposed on a rotating molecule he quantized in units of h/2ir.
there are
arises
27
BJ{J
1).
The number 27
from the states with angular momentum components of 7, 7 1, 7 2y. 0, 1, 2,.. . 7 + 1, 7 times h/2r that would appear if an external field were applied. In view of this 27 + 1 degeneracy of the 7th energy level, the Boltz
mann
levels is
Nj =
It will
(27
/!
(14)
be seen later that the allowed rotational energies typically have small energy spacings compared to the roomtemperature value of
For example, N has an N N bond length of 1.126 A and an N O bond length of 1.191 A. The moment of inertia can be calculated,
kT.
2
lO40 g
cm 2 and
,
at
25C
is
Nj =
(27
(15)
N2
at 25C.
AV^o
10
15
20
25
30
35
40
45
Rotational
quantum number, J
54
The
that, in
HC1
Make
34. Rotational
when the
The first requirement for the absorption of radiation by a rotational energy transition is that the molecule must have a permanent dipole. The rotating dipole can be thought of as interacting with the electric field of the radiation and allowing energy to be exchanged between the moleand the radiation. The requirement is seen to be equivalent to that stated in the previous chapter where the vibration of a molecule had to be accompanied by an oscillating dipole for such interaction to
cule occur.
There
is
molecules which have dipole moments. The selection rule for rotational transitions of linear molecules that occur with the absorption or emission
of electromagnetic radiation
is
AJ = 1
For
ably done
(16)
when
AJ = +1.
and the population
results obtained in the
With
by the
vertical
arrows of Fig.
35.
general expression for the energies that are absorbed in the transitions indicated by arrows in Fig. 35 can be obtained from the
The
If
the
quantum number
for the
lower level involved in a transition is J and that for the upper level is 1 and therefore the value of f for the J 1, the energy difference in cm
absorbed radiation,
v
is
2)
 BJ(J +
l)
( 17 >
OF
LINEAR MOLECULES
55
We
0,
1,
2,
will generally
4JB,
be
. .
&B,
and should therefore observe a set of lines spaced by a constant amount. This amount can then be identified with 25. One observes in the microwave spectral region such series of absorption lines when linear molecules with dipole moments are studied. Table 31 shows the frequencies of absorption, attributable to rotational transitions, observed for the Unear molecule OCS.
FIG. 35
Rotational
is
transitions
for
rig id rotor
linear
molecule.
The symbol B
30B
Ai=105
Spectrum
56
From
line
S =
12 16
2( 2 9 9 790
Z)
20285
^
of inertia of the
(18)
Therefore, since
B =
moment
OCS
mole
138.0
10 40 g
cm 2
(19)
should be apparent that from this single experimental result it is not possible to deduce both the CO and CS distances of the molecule. In such cases, what is done whenever possible is to obtain the rotational
species.
12
32
berg, Wentink,
Rev., 75:
and and
= =
138.0
X X
10 40 g/sq
cm
cm
(20)
0.197910
cm
7 0l6c i 2s 34
141.4
lO" 40 g/sq
lengths are independent of the isotopic species, one deduces that in the
OCS
molecule
r(CO)
r(CS)
= =
1.161
1.559
0.001
0.001
A A
(21)
one will discover, to verify that these distances are conmomentofinertia data than to derive the bond lengths the sistent with
It is easier, as
from the moments of inertia. Measurements of the spacing of rotational spectral frequencies have
Absorptions of TABLE 31 the Microwave Region Due
Transitions*
16
C 12 S 32
in
to Rotational
Transition
Frequency
J +
>
(megacycles/ sec)
0
24,325.92 36,488.82 48,651.64 3>4 60,814.08 4>5 * From Wentink, and Strandberg, Kyhl, Phys. Rev., 75: 270 (1949).
l>2
2* 3
H c a
OF
LINEAR MOLECULES
57
moments
bonds of molecules.
Some
shown
in Table 32.
Close examination of data such as those of Table 31 reveals that the
is
The constant spacing expected from the treatment given here is that obtained from the rigidrotor approximation. Now we can see (although this is a minor matter that can be passed over) what alterations to the
theory arise from the recognition that molecules are not rigid, but are flexible, and can be expected to stretch under the influence of the centrifugal forces that aris&when
they rotate.
Exercise 33. The rotational constant term B = cB is given by Gordy, Smith, and Trambarulo [2] for HC 12 14 as 44,315.97 megacycles and for
Deduce moments of inertia for these molecules. Assuming that the bond lengths are independent of isotopic substitution, calculate the H C and C N bond lengths.
as 36,207.40 megacycles.
DC N
12
14
*35.
The stretching effect of the centrifugal forces on the bond lengths, and therefore on the moment of inertia of a rotating system, can first be calculated on the basis of classical behavior. Consider, for simplicity,
Some Bond Lengths Obtained from wave Spectroscopy of Linear Molecules*
TABLE 32
Micro
Molecule
Bond
Bond
distance (A)
1 1282 2.3606 1.064 1.156 1.629 1.163 1.052 1.211 1.632 1.057 1.203 1.382 1.157
.
CO
NaCl
C=0
NaCI
HCN
C1CN
HC=CC1
HC^CC=N
c C=N
*
From W. Gordy, W.
barulo,
Sons, Inc.,
New
York, 1953.
58
m rotating
that,
Assume
when
a distance r from the fixed point and that this length increases to a
value of r
when the
particle rotates.
The
k(r
centrifugal force of
stretching
www 2 is balanced by a restoring force of that accompanies bond stretching. The extent of bond that occurs for an angular velocity of w is, therefore, given by
the expression
k(r
= www 2
(22)
On
= _Jr k rrua*
is
(23)
made up
of kinetic
and
= Jw 2 +
ik(r
r)
(24)
2
2
Iu>
+ +
2~~
= I
7o)2
I(W
2
fcr
2
(25)
The quantum
tized according to
momentum
I<a
be quan
y/j(J
1)
(V2t)
to a quantummechanical result.
therefore, deduced to be
The
=
which
^^
of
1)
32^^ +
1)2
(26)
major importance in Eq. (26), to r by means of Eq. (23). In this way, and approximating r by r in the second, minor term of Eq. (26), one obtains
is
tj
'(' + ^D gSSFT^
"2
'
.J^'V +
3ar*mVJIb
l)'
(27)
OF
LINEAR MOLECULES
59
= BJ(J +
where
o>
1)
J*(J
1)*
(28)
is
s/k/m
and, as before,
B = h/WIc.
It is
customary to write
energy
levels as
tj.
= BJ{J
1)
t)J\J
1)2
(29)
where D, known as the centrifugal distortion constant, is a quantity that can be evaluated from spectral results and, according to the above
by the
D =
difference
4B>/tf
of
(30)
The value
is
always very
between the
rigid
than that of B, and the and nonrigid rotor treatments can, as Fig. 36
less
much
J 8
ft
5
FIG. 36
distortion
shown by the comparison of the allowed rotational energy levels of a rigid (solid lines) and
nonrigid (dashed lines) rotor.
Rigid rotor
Nonrigid rotor
60
TABLE 33
Transition
HQ*
\>b
.,
J+J +
3>4 4>5 5>6 6>7 78
8* 9 9> 10
10
*
(cm" 1 )
83.03 104.1 124.30 145.03 165.51 185.86
(with
Pcalc
(B
11
206.38 226.50
of
suggests, be expected to
levels are
involved.
The
AJ = +1
Eq.
(29),
Ai(J  J
+
of
1)
= 2B(J +
1)
4D(J
l) 3
fit
(31)
The data
distortion.
Table 33
illustrate the
improved
to experimental
for centrifugal
by allowing
PRINCIPAL REFERENCES
1.
3,
D. Van Nostrand
Spectroscopy,"
Company,
2.
Gordy, W.,
John Wiley
W. V. Smith, and R. F. Trambarulo: "Microwave & Sons, Inc., New York, 1953.
THE ABSORPTION
AND
EMISSION OF RADIATION
In the two previous chapters it has been necessary to state, without adequate explanation or proof, that transitions between allowed energylevels can occur with the absorption or emission of electromagnetic
radiation.
an thus occur have been quoted. Now that some introduction to lowed energy levels and to simple spectra has been given, it is approprie to investigate the theoretical basis
>e
understood.
considerable
amount
The
however, an expression that can often be used in a qualitative, or diagrammatic, way to understand what transitions will occur in a particular
band that
and
41.
system and, moreover, the intensity of the absorption or emission will be observed. (The reader will notice that in the previous
chapters the emphasis has been on the frequencies of absorption bands little attention has been paid to their intensities.)
trated
and
illus
known
as the timeinde
A more complete expression for Schrodinger's equation allows the calculation of atomicscale phenomena as a function of time as well as of space. For one dimension the equation
pendent, or amplitude, equation.
written for x and
t is
_ v
a*9(z,t)
U(xn(xt)
_ _
j_g*M
m
61
The
will
is
a function of x and
t,
i.e.,
^(x,t),
not be continued.
t
be understood that
x.
is
a function of x
and
and that ^
is
a function only of
Previously
it
i.e.,
gave
In a similar way,
***
and time.
To reduce
tion to
into
more manageable forms, it is customary to try to separate them two equations each involving only one of the variables. With this
tries the general substitution (2)
approach one
=
where
*(*) (f)
4>(x)
and
<f>(t)
are functions of x
and
t,
respectively.
Substitution
is
a function
only of
x, gives
&*&*> + "**>&*(*!&
or
'(x) [ <Kx) L
2
(3)
8ir
dx 2 J dx*
+ ^
17(35) v
'
= 
1
<*>({)
d*(<)
dt
x,
2ti
The
x and
since
t,
equation
t.
is
a function only of
and the
right
only
if
each side
is
it
can be identified
The equation can be valid for aH values of equal to a constant. The constant is called e with the energy of the system. The two
(3)
are
4jja
and
*,
+
U(x)f
(*
A 2 dV &w 1mdx i
e+
(5)
The second of these equations can be recognized as the timeindeThe timedependpendent Schrodinger equation introduced in Chap. 1 ent part of the complete Schrodinger equation can be readily solved, and
.
the solution
<t>(t)
is
e< 2 "'>'
(6)
where
is
involve a
THE ABSORPTION
63
*(:r)e< 2 "'
(7)
solutions that
one thinks of the particleinabox problem as an example, the would have been obtained from the timedependent Schro
*,(x,0
J^in^U'
nn
8ma 2
2 "'")'"'
where
(8)
The implications of the solution in x and t can be seen if the quantummechanical description of the system, as given by **'4 is obtained.
r
,
This
is
given in general by
\j/*\
= =
,)
' <
*V
of the solution to the space
is
(9)
seen, therefore, to
again described
that are time independent, are said to have allowed stationary states. These are the allowed states that are obtained as solutions to the timeindependent Schrodinger equation.
exist
which
How
now be
42.
investigated.
Much of spectroscopy is concerned with the absorption of radiant energy as a system goes from one stationary state to another under the
influence of incident electromagnetic radiation.
tigate, therefore,
It is necessary to inves
how
system so that a transition is induced. In general any atomic or molecular system will have many allowed energy levels corresponding to the stationary states of the system. It
64
is sufficient,
and the notation is simplified, if a system is treated that is assumed to have only a lower energy state, with a wave function and an upper energy state, with a wave function m where I and m are two different values of the quantum number for the system. The complete time and space Schrodinger equation for one dimen\[/i,
\f/
,
sion
is,
as before,
8w 2 m dx*
+
'
= U(x)* K '
 ^.^2wi dt
symbol H,
(10)
d2
8w 2m dx 2
(Although
that
it is
+
,
TT , U(x)
it is sufficient
to treat
system.)
With
this notation,
The
$1
by
and
yp
m exist for the system implies that the only two solutions to
and
(12)
Since such solutions to the Schrodinger equation, as pointed out in Sec. 17, form an orthogonal set of functions, a general solution to the equation
can be written as a
two solutions
exist,
is
simply
(13)
* =
t
a&i
am ^r m
where a and am are weighting coefficients which are not functions of x The two allowed stationary but, as we will see, can be functions of time. states of the system are described by the general expression with Oj = 1,
am
or a
0,
am
1.
The potential energy of the system before it is disturbed, or pert turbed, by electromagnetic radiation is now represented, more specifically,
THE ABSORPTION
65
by
Uo,
H 'a' +
as
ff
case
is
(14)
then written
(15)
Now
let
us assume that
I t
it is
with the
known that initially the system is in wave function j and energy ei. The
by Eq.
(13),
at time
0.
0,
is
therefore described
with
and am =
and energy
is
;.
This state of
i.e.,
undisturbed,
as long as
U =
J7o.
Now
tem,
let
falls
on the
sys
As
will
radiation
may
be shown later in more detail, the electric field of the act on the system and change the potential energy. The
U' and that in
H'.
change in
U is denoted by
is
H is denoted by H'.
and i
The new
will
Hamiltonian
satisfy the
then
Hq
The
is
differential
therefore changed,
new
equation.
The more
general expression
* =
ai{t)* t
am {t)*m
(16)
where O; and am are timedependent parameters, can be used to provide a solution to the new Schrodinger equation that is applicable to the perturbed system.
This wave function, with undetermined a and o m can be substit
,
to give
(#o
H'Haflr,
am * m )
= 
AA
(,*,
o*m )
Expansion of
a
H .*, +
am
H *m +
"
dt
2wi
dt
2ri
am
d^m
~dT
'
66
The
fied
two and
last
Wm
are solutions
is
of the
The remaining
expression
simpli
if it is
from
x= >tox
+00.
by V* and integrated over all space, i.e., The orthogonality of ^m and fa eliminates
one of the integrals, and the timedependent part drops out of the ***, integral as in Sec. 41. On rearranging the remaining terms, and
substituting Eqs. (12), one has
da"
dt
? fljer<
h
, H/A)
_ m)
^H h dx
,
~
It is
2m
h
/"+
known
that initially a
not
initially contribute.
It
final final
dam
dt
2
e
(19)
This important equation gives the rate at which a system can be changed from one stationary state to another under the influence of a
perturbing
rate at
which a m increases corresponds to the system changes from fa to m To proceed it is necessary to be more specific about the perturbation H'. Some features of the interaction between the electric field of the electromagnetic radiation and the molecular system that absorbs
effect.
The
rate with
of the
\[/
now
treated.
When
electromagnetic radiation
state, here
will
assumed to be characterized by the quantum number I. It be recalled from the discussion presented in the introduction that
field of
the electric
equation which
is
usually written as
(20)
E.
= 2E X
cos 2wvt
It is here
THE ABSORPTION
Ex =
The
(e 2 ""
e*')
(21)
component
At
actions in the y
can be added on. can act on a dipolemoment component /** This term adds to the potential to produce a change in energy of E x n x that occurs energy of the system and is responsible for the change in
and
z directions
The
electric field
Ex
when
One can
write, therefore,
(22)
H' =
If
ExP x
,
Ex is
shown
explicitly, this
becomes
(23)
H'
(e 2 ""
ei*
M )nx
^2 =
(t
~E
th
+" f tltx^i
00
da;(e< 2
* i "'>'+A'><
e (*r/ .,<)
(24)
The
by
\n x im\; i.e.,
Im.1
/_*"
Kn*h dx
and integration
to
(25)
With
this notation,
one obtains
1
p(.2Tilh)(e m ei+hv)t
ti
xr + hv
is
+.
_
e
>(2irtM)(,fc>')!l
e{
hv
(26)
J
The
lower energy level u to a higher one e m For such an arrangement of energies, the denominator of the second term in the square brackets
will
is
such that
(27)
e,
For such conditions this second term can take on large values and be of major importance in determining am (t). On the other hand, if tm were lower than t t the first term in the square brackets would be of major
,
differ
*8
to
is
term one
of emission, whereas the second term is important if the transition is one of absorption. Since we are here investigating an absorption process, the energy of the to state is greater than that of the I state, and it is only
necessary to retain the final term of Eq. (26). the assumed energylevel pattern
[1
We
t>iirilh)ii m T\,)t~]
described
As the system changes from the description ty to *m it can be by the product *&, where * = a&i + am ^rm and the a's are
,
time dependent.
tion,
as a function of time
This quantummechanical description can be given if it is integrated over all values of x. This integraall
moreover, removes
the spacedependent
of their orthogonality
and normalization.
l
One
is left
/_"
*** dX =
ai
am a
29 )
is is
The importance
given, therefore,
of the
mm HEIY
L
(e m
ei
1hvy 
(3o >
rrtwi
The above
Integration over
all
E x as a constant
since the
absorption will usually occur over a narrow frequency range, gives, with the definite integral
+"
sin 2 x
/:
the result
5 ax
,
a* m {t)a m (t)
\ii* m
\KK)H
(31)
This
radiation
is
is
by
strength instead of
its
energy density.
It
when comparisons
amount of radiation that is more convenient made with experimental determinations of the
THE ABSORPTION
69
amount
of absorption.
is
The necessary
relation,
which
is
out derivation,
^ (KY
the energy density,
i.e.,
(32)
where
p is
is
irradiated
radiation.
(31)
by
in the description
Jt
w
= =
*ft.
(33)
For isotropic radiation the three components interaction are equal, and one writes
of the radiationdipole
(oOm)
jjj
\(Hxlm)
{HylmY
G*lm)*p
%
,
wV
(34)
B tm
becomes
(35)
J (OrnOm)
t
= B lmP
with
8ir B tm = gp Wm 2
 
(36)
by j shows the
The
\fn m \, moment, and on the energy density of the radiation. To complete the general study of the process by which radiation energy is absorbed, it remains only to compare this derived expression
with the quantities usually encountered in the experimental determinations of the absorption of radiation.
70
Exercise 41.
sin 2 (2ir/h) (e m
(.
hvY
;
hv)
which must be integrated over all frequencies to obtain Eq. (31), versus frequency near hv = e m n, and see that the frequencies that contribute most to the integral are those close to the Bohr condition em e = hv.
t
44.
The
an absorbing solute
in a
it
nonabsorbing solvent.
dl,
The
as in
penetrates a distance
I,
the radiation
dl.
and
coefficient,
dl =
by writing
a(v)IC
dl
(37)
to be written.
The dependence
of a
on the frequency
is
here emphasized
cell
a(v).
length
,
the
I,
cell
containing
The
is
obtained in this
way
aOOijln^
FIG. 41
Source
(38)
solution.
Spectrometer
ir dl
Solution of concentrate,
moles/liter
THE ABSORPTION
71
An
range of frequencies.
absorption band for a given transition usually extends over a The total intensity of the band is obtained by
measuring a(v) in the region of the absorption and determining, usually by graphical integration, the integrated absorption coefficient A, i.e.,
a(v) dv
(39)
A =
J over band
a(v) dv
= A
c
It is
now
The
transfer of molecules
from state
!
to state
m is
(40)
(B (.)p
If
iW
one introduces the symbol N' to represent the number of molecules in a cubic centimeter of the sample and recognizes that an amount of energy hv tm is removed from the radiation by each transfer, the decrease in intensity, or energy, of the beam passing through a length dl of the
sample
is
dl = p Wm V^JV'

(41)
Furthermore, since /
of 1 sq
is
cm
in 1 sec,
it is
by
(42)
cp
Equation (41)
dl = Wm 2 ()
 
hv lmN' dl
(43)
For comparison with the experimental expression, Eq. (37), it is If Avofinally necessary to relate N' to the molar concentration C.
gadro's
number
is
N,
this relation is
N'
= NC
1,000
(44) ; v
72
 d7
Sw@^S a
differential
(45)
(37),
The theory
than
made with
A =
ja(u) dv.
In this
way we
2
obtain
3/ic(l,000)
yjmlWml
(46)
where
v tm is
it
will
be recalled,
47 )
iMtml
= /_ T **"* dx
result given
The important
for a transition
if
by Eq.
(46)
is
wave
Conversely, if the integration of Eq. (47) can be performed. one can use the measured value of A to obtain a value of ju; m 2 and of + /xim and thereby learn, by means of Eq. (47),. something about the

known and
wave
In subsequent
be used.
The
between the transition moment of the absorbing species and the absorp
by a given sample. From this relation, furthermore, some very important qualitative statements can be made about which transitions can be induced by radiation, and thus lead to the absorption of radiation, and which transitions cannot be so induced, and therefore fail to absorb radiation. Such general statements are called selection rules, and for a given system they can be deduced by deciding for which transitions the integral \m m must necessarily have a zero value. The deduction of selection rules for the particleinabox system will
tion of radiation
often
The
dipole
moment
THE ABSORPTION
will
73
ey
is
(48)
with n
For a transition from a state with = ItO one to be induced by electromagnetic radiation, the integral
W=
The
/_^ 2
MejMm <*z
(49)
must he nonzero.
integration will be carried out in the next section
is
desired.'
here illustrate that for the deduction of selection rules it is often sufficient that appear to consider the symmetry of the three functions if/*, ey, and
in
Eq.
(49).
The coordinate system, of Fig. 42, with y at the midpoint is convenient for the symmetry discussions that are necessary here. The coordinate y, and therefore the function ey, is clearly an odd, or antisymmetric, function since
it
All the
wave
(odd function)
FIG. 42
wave
tranrule
function
74
functions, as
was shown
i.e.,
product of the three functions of the integral of Eq. (49) is an odd function, the result of the integration over the left half of the potential well
will exactly cancel the contribution
half.
\
Thus \m m will necessarily be zero for a transition from n I to n = m if I and m are both odd numbers or both even numbers. The
allowed transitions,
state with
i.e.,
the transitions for which \m m is not necessarily with an even value of the quantum number to a
\
an odd value.
recognize that the selection rule stating that transitions
One should
can occur between energy levels only if one level has an odd quantum number and the other an even quantum number is equivalent to the statement that only levels of different symmetry can combine. The
selection rule can be conveniently expressed as
+
where
<+>
+,
(
wave
wave function and The transitions
function.
As for this particleinabox example, it will often be possible to deduce selection rules without a detailed working out of the integrals. The symmetry of the system will be important in this regard, and the
selection rules will usually
metry
A6.
in
of the
have some simple direct relation to the symwave functions corresponding to the energy levels.
Particle
To
transition,
/*j].
The
transi
for
For the dipole moment term p. one writes, using the coordinate system which the wave functions of the square well were given in Sec. 15,
/
1{'
I)
ex
ea
(50)
The wave
functions are
.
*
sin
\ja
nwx a
(51)
THE ABSORPTION
75
and the
,
transition
,
moment
\tu m
is,
therefore,
2e
Mi*
Since the orthogonality condition eliminates the integral arising from the a/2 term, one
is left
I"'
Making use
sin B sin
= Mcos
(0
*)
cos (0
<)]
(54)
one gets
ImiI
 l" a Jo
x cos
(I
m) a
x cos
(l
m)
\dx
y
(55)
Integration,
making use
"J = cos dy y
y sin
y,
gives
ea
Ml*
I"
I
cos
(I (i
i*
m)ir  my
I
cos
(I
(J
+ w)7r 3 +m ]
2 )
(56)
m and + m
The
selection rules
and m.
specific
The
can be used as a
The
4.
transition, as Fig.
sponds to
gives
. .
3 and
m=
96 ea
^ 2ea
is
~~
(
The
(46), as
8**N
3Ac(l,000)
""
4e 2 a 2 **
(58)
_ 32NeWvlm
SwhclflOO
Using X (lB
2,600
and a =
7.3 A,
one gets
A =
14
10 18 sec 1
cm1 mole1
liter
76
A =
is
Ja(v) dv
4.3
10 18 sec" 1
cm mole1
liter
Exercise 42.
absorption.
same number
of molecules
many
molecules to go
from
from I to to. No net absorption of energy will be observed. In practice, when one studies absorption spectra, one generally deals with a system where each state of lower energy has a larger population than each upper state. A net absorption of energy is then observed.
I
m to
as
bility of
In addition to induced absorption and emission, there is the possispontaneous emission. The probability of such emission is
usually
here.
and
it
Finally it can be mentioned that the treatment of induced absorption has been based on the interaction of the electromagnetic radiation with the dipole moment of the atom or molecule. Emission or absorption
can also occur as a result of the quadrupole of the atom or molecule. The interaction of the quadrupole with the electric field of the radiation is smaller than the dipole interaction by a factor of about 10 8 and one can therefore almost always ignore these quadrupole effects.
,
48.
The treatment
in
of vibrational energies
Chap. 2 used the selectionrule result that for a vibrational transition to be induced by electromagnetic radiation Av = +1, where v is the
vibrational
quantum number.
It
can
\ii
now be
\
= 1
can
tm
nonzero.
The
application to a vibrawill,
problem
of the
how
77
will
ever, be demonstrated.
An
important result
be obtained by a
derivation of the relation between molecular properties and the amount of to v 1 vibrational absorption caused by the fundamental v =
transition.
In Sec. 44 the result was obtained that the integrated absorption
coefficient
(y)
l
dv
Jo
dv
see
1
cm1 mole1
liter
is
moment
*
A 
31^0)
vM
SeC_1
Cm_1
mle_1 Uter
In the experimental study of vibrational transitions one usually deals 1 with frequencies v, with units of cm 1 instead of v, with units of sec
, .
In terms of
v,
is
1
3Rlfj0)
v
^W
are
I
nudcr^
liter
(59)
For the fundamental transition for which the values of the vibrational
quantum number
Ao1
0.
and
m=
1,
is
=
3h!(lfi00)
i>
lM l12
(60)
The dipole moment, necessary for the evaluation of moi, of a heteronuclear diatomic molecule must be expected to be some not easily
determined, or even expressed, function of the internuclear distance. It is possible, however, if it is required that" the dipole moment must be
expressed only for small displacements of the molecule from its equilibrium configuration, to represent the dipole moment by the series
expansion
m
(61)
where
perma
displacement coordinate
(62)
= rr,
78
"='"
(!) 9_
9+

()
The wave functions for the v = and the v = 1 states that are involved in the fundamental transition are shown in Sec. 24 to be expressed in terms of the displacement coordinate as
*
~ aqm
and
where
2t \/iwfc 4x 2iu d .jic
and
/i d
is
it.
moment
With these
can be set up,
IMoi
if
only the
first
and ^ x the transition moment p, ^ two terms of Eq. (63) are retained, as
, ,
/_
(64)
and ^i leads to a zero contribution from the and shows that a constant dipole moment is not sufficient to lead to a vibrational transition being induced by electromagnetic radiation. A nonzero value of moi can, however, result from the second term of Eq. (64). This leads to the result
of ^o
The orthogonality
constant term
/j g
aa!
(65)
The
i
o
Xi
^" dx
= i^ta
<
66 >
One obtains

Wl =

_i=()
(67)
THE ABSORPTION
79
and with
moment
coefficient
is
inS^(%l V A=
3c 2 (l,000)Mred.
m
(69)
or
_ ~ *
3c 2 (l,000)Mred.A
*N
important result that shows
is
Equation
ties Ma.
(68) is the
how
the absorption
and
The
transposition
is that which is used when dipolemoment derivative from the measured absorption intensity. The measured value of A for the fundamental transition of BrCl 1 at 439 cm for example, has been reported by W. V. F. Brooks and B. Crawford [J. Chem. Phys., 23: 363 (1955)] to be
A =
From
105
14
cm 2 mole
liter
(70)
this value
of 4.1
102 *
g,
one calculates
(71)
\dg/=o
10 10 esu
Although distortion of a chemical bond from its equilibrium distance undoubtedly generally accompanied by a complicated redistribution of the electrons of the bonded atoms, the order of magnitude that is to be expected for values of (dn/dq) q= o can be obtained by assuming a
is
constant charge of
atom.
M
With
this
+ be on one atom of the bond and model the bond dipole moment is
r
be
on the other
(Se)r
(72)
r
and, since g
\dr) r=r
~
,
~
\dq) qa
This result suggests that values of (dn/dq) q= o should be of the order of magnitude of the electron charge, 4.8 X 1010 esu. The result obtained
for
BrCl
It
is
attempt to express the dipole moment of a bond, or a diatomic molecule, by means of Eq. (72). One can, however, recognize that at r = the dipole moment /i is necessarily
is,
80
o,
media essen
particles, n is also
zero. The value of n at the equilibrium distance can be determined, but even this determination does not lead directly to a determination of the
moment.
The information
available,
of A, can be illustrated by the curves for possible dipolemoment versus bonddistance dependence shown in Fig 43. It is at present a difficult matter
to decide whether the curve with a positive value of (dn/dq) q= o or a negative value is correct for a given molecule. Nevertheless, the measof values of A and the deduction of values for (dn/dq) = a q according to Eq. (71), lead to the accumulation of data that are of con
urement
molecules.
49.
The
Intensities of
molecules that lead to the absorption of radiation, usually in the visible or ultraviolet regions, will not be given until Chaps. 10 and 11. It is,
bands that
result
from
electronic transitions.
The
calcur,
lation
is
molecule or ion.
is
assumed
With
FIG. 43
Types of
ft
fi
and
dn/dq.
Mobs.
g
0 +9
THE ABSORPTION
81
wave func
Each
Now, however, since p.x = ex, y.y = ey, and p, ez, by e, and so forth. Likewise, since the mass of the electron is much less than that of the remainder of the molecule, one replaces /tw. by m, the mass of the electron. With these variations the transition moments for this simple model of a bound electron are,
that of Eq. (67).
(d/u/dx) x _o
a,
IMoii!
ImJ
*S^
(74)
3e 2 ft
8ir 2 TOvC
Moi'
(75)
(46)
A =
or
A
iVe 2
tt^f.
1,000cm
sec
1
cm1 mole1
liter
(76)
Ne 2
n n , l,000c 2 wi
*
cm
2
,
mole
1
liter
A =
Ja(v) dv
is
2.31
10 8
cm2 mole1
liter
(77)
This result
this
To do
one introduces the term oscillator strength. This is denoted by / and is denned as the ratio of the observed integrated absorption coefficient Thus one has to the value predicted by Eq. (76).
,
= =
Ua(v) di>U,
[iVe 2 /l,000c 2 m]
4.33
10 9 /a(i;) dv
(78)
One
very
finds, in fact,
that
many
/,
electronic absorption
One
much
smaller values of
and
in these cases
These ideas
11.
82
PRINCIPAL REFERENCES
1.
Pitzer,
K.
S.:
"Quantum Chemistry,"
1953.
chap.
6,
wood
2.
Cliffs, N.J.,
Quantum Mechanics,"
6,
3. Slater, J.
McGrawHill Book Company, Inc., New York, 1935. C: "Quantum Theory of Atomic Structure," vol. 1, chap.
Inc.,
Mc
New
York, 1960.
ROTATIONAL SPECTRA
Some
states
of the principal features of the
and
in
Chap.
The
rotational energies
treated under headings that specify the relative value of the three
principal
is
moments
On
asymmetrictop molecules.
of linear molecules
have already been dealt with in Chap. 3. Now the heading will be used principally to introduce a number of finer features of rotational spectra that were not mentioned in the earlier introductory
chapter.
LINEAR
MOLECULES
The selection rules for transitions between rotational energy levels and the multiplicity of these levels have been stated in Chap. 3. Before
proceeding to molecules of general geometry,
simple situation of linear molecules.
.
it is
perhaps advisable to
look in somewhat more detail at these two features for the relatively
observed in
when
nuclear spin,
if
molecular rotation and for commenting on the effect that any nuclear
spin has, as a result of the statistics that are followed, on the rotational
states that exist.
83
84
Molecules
The requirement that a molecule must have a permanent dipole moment and that the rotational quantum number can change only
by one unit for a rotational transition to be induced by electromagnetic radiation must first be investigated. As was shown in Chap. 4, to do
this it is only necessary to investigate the value of the transition
moment
The
the dipole
moment
The
rotational
somewhat intricate and can be found in any of the standard texts on quantum mechanics. The problem is, as was mentioned in Chap. 3, generally solved when the hydrogen atom is
be given here since
it is
studied.
It turns
two
parts.
One part
and
move about a
nucleus.
set
The former part is identical to the equation that up for a freely rotating rigid molecule which, of course, would
of these equations
The correspondence
rota
tional
wave
hydrogenatom wave functions. These are where both the J quantumnumber notation appropriate to molecular rotation problems and the s, p, d, notation
familiar angular part of the
illustrated in Fig.
51,
. .
.
will recall
related to functions
solution
is
known
as
Legendre
functions.
Each
characterized
by
two quantum numbers which are here denoted by J and can be assigned integral values, with the provision that or equal to, /. The wave functions corresponding to some
energy states are given in Table
51.
of the lowest
problem leads to allowed energies that are identical to those given in Sec. 32. The solution functions illustrated in Fig. 51 and Table 51
CM
i
V >
"5
= o o
B
e
a.
a S E
o
i5
o
r
"l".
HI
85
86
8wU
This result
angular
is
J(J
1)
/ =
0, 1, 2,
(1)
momentum
Furthermore,
if
quantummechanical
momentum
average angular
it is
found that
Total angular
momentum =
\/J(J
1)
h ~
Component
TABLE 51
Molecule
of angular
(2)
Some of
the
=0
Af
=0
=
= +1
1 <P
2Vi
7=
/ =
M
Af
,=i^COS9
* =
8mee 2\l%r /i 5
\
1/3.
I
OT
 */sin
2
'""
9 cos
4>
S 1 1
1
..
/3 /sin 9
sm *
J 
M M
^ = ./i,
2 (3 cos
91)
or
4 \ir
.
 1
9 cos 96*'*
/l5
.. /
<t>
1 1 1
/1 5
.. /
2
/
sm
9 cos 9 sin
.. *
IT
Af
= 2
&,
4 \2ir
/ 1
I
sin
/l5
../
9e 2i+
or
) /
I
sin
IT
9 cos
2*
1 (15 / sin
9 sin 2c>
jr
ROTATIONAL SPECTRA
87
where
M=
0,
+1, 2,
is
J
now familiar total angular momentum stipulation, momen
The first of
these
the
tum component
It is
in
sometimes convenient to illustrate the angular momentum components implied by the rotational wave functions by means of
a vector diagram.
of
terms
+ 1) and are illustrated in Fig. 52. The number of angular momentum components along an axis that can be obtained from a given value of J can be seen from such a diagram to be 2 J + 1.
\/J(J
Exercise 51.
momentum
to the
J = and +1 wave functions, and confirm that momentum is y/J(J + l)(h/2ir) in these cases.
After the
wave functions
is
is
moment
integral
of the molecule
is
represented by
FIG. 52
The
total
2.
For 1
an applied
2)
More
states
would be revealed.
Angular
momentum
in direction
component
.
Angular
momentum
of
rotating molecule
KA/27T)
2(ft/2T)
'
88
any orientation
of the molecule,
by
Mx
nv
y. t
= = =
mo sin 6 cos
/xo
4>
sin 6 sin
<f>
(3)
mo cos 8
of Table 51 and the dipoleone can investigate the contributions of the transitionmoment components to the total transition moment. In this way, if a transition between a state characterized by J' and
With the
rotational
wave functions
(3),
moment
expressions of Eq.
M"
gj n
fl
is
MQ
Mo
2 f '
^J'M'
[J
2
CQS
^J'M" gm
(20
df d
(4)
^j'Mjjf'i
J'*<j"<jf"
=
=
'
o Jj
2x o
j" ' o
fw
sin 8 sin
W"*" sin
de
dtf)
dfl
Mo j"
(It will
dd
d<t>
in polar
coordinates.)
transition
of
the total
moment
lJ"Af'J"ikf"2
(5)
It is
(4)
moment
for
It
requires a
J'
J"l
(6)
that
is,
A/ = +1
The deduction
JMolecules,"
of
this
result
is
outlined
in
"Spectra
of
Diatomic
by G. Herzberg, and
will
The verification
ever,
suggested as exercises.
Exercise 52.
51
Deduce from the symmetry of the wave functions of Fig. and the antisymmetric nature of the dipole moment, as can be verified to J = 1 will be from Eq. (3), that the transition moment for J =
nonzero while that for the J
to
J =
ROTATIONAL SPECTRA
89
Since the energy of a freely rotating molecule is, according to Eq. only on J, the selection rule for J is of prime importance dependent (1), When, however, as will be discussed in the in rotational spectroscopy.
next section, an external electric field imposes a direction on the rotating have different energies molecule, the states with different values of
and the
M M becomes significant.
It is
AM =
(7)
Again, since the general proof of this requires a knowledge of the behavior One can, however, verify of spherical harmonics, it will not be given.
that this selection rule operates for transitions between states described
of Table 51.
Verify the
AJ = 1 and
the
AM
J =
to
J =
transition.
of the rotational spectra of generally
The treatments
other selection rules.
shaped moleit is
cules that will be presented in the remainder of the chapter will introduce
These
will
3.
in
Although the rotational states of linear molecules are characterized two quantum numbers, the energies of these states depend only by The 2J + 1 the on total angular momentum quantum number J. degeneracy of these rotational levels, due to the various values of for a given value of J, can be made apparent if an external field is applied
is
observed.
An electric
used,
and the
shifting
and
results is
gives the
component
field.
of
the angular
momentum
in
an applied
is
direction,
and
in a Stark effect
experiment
states with
this direction
electric
The
different values of
it
these different orientations relative to the applied electric field will cor
The
90
M experience
is,
is,
The
as will be
The
of this
treatment and
is
outlined,
with references, in
ized
Se,
ref
The result of the calculation is that the energy of a state characteris shifted in an electric field of volts/ cm by by values of J and
where
for
?*
01
4,'IgjS*
fe
J(J
1)
(300)
J(J
1)(2J
 3M  1)(2J +
3)
e g
while for
/ =
(8)
= "
00P
er
&
can be converted to frequency
shifts of
These energy
shifts in ergs
cm1
spectroscopy.
The
effect
on the energy
shifts
levels given
by
these equations
is
shown
These energylevel
rules
show up when
field.
Now, both
selection
AJ = 1
or, for
AM = AM =
(9)
absorption experiments,
(10)
AJ = +1,
With these rules as mentioned in the previous section, are important. the allowed transitions can be added to the energylevel diagram, and this is done in Fig. 53. Observation of the number of components that
rotational line splits into
when an
it
a great
In Chap. 3
series of equally
obtained.
While
this is
a rotational spectrum of a linear molecule true for linear molecules, sufficient complexi
ties are
ROTATIONAL SPECTRA
91
molecules that a simple matching of the spectral lines with the expected
pattern
is
seldom possible.
effect,
measurement
(8),
the determination
.
FIG. 53
field
of HCI.
200
6X
y
10 6
=4
150
M
0
4X10 6
= 3
1

3
+2
100
E u e
M
2X
10
^^^^
so
J
^
.
M = l
50
M=
No
applied field
1,000 volts/cm
2X
10
92
D. K. Coles [Phys. Rev., 70: 560 (1946)] for the molecule OCS.
oscilloscope pattern of the
The
J =
to
J =
2 line
is
shown
for different
made
using
= 1 energy level (a) Calculate the shift in the J = 1, as a result of an applied electric field of 5,000 volts/cm. (b) Estimate from Fig. 54 the dipole moment of the OCS molecule.
Molecular Rotation
It
53.
Nuclearspin Coupling
+
has been recognized that the allowed rotational st ates of a mole1) *yP e cule are those for which the angular momentum is a \/J(J momenangular rotation molecular this to addition In h/2*. multiple^ of
tum, some molecules have angular momentum because of the nuclear A complete characterization of the spin of one or more of their nuclei. as we will see, must take into account molecules, such of rotational states both the molecular and nuclearspin angular
to the total
momentum
contributions
angular momentum.
One
finds, in fact,
experimental evi
dence in the hyperfine structure of rotational transitions of some moleThe basis and nature of this fine cules for the effect of nuclear spin.
detail of rotational spectra will
here
is
be only briefly outlined. Its introduction to appreciate the many rotational student intended to allow the
spectra studies reported in the literature where this effect occurs. The angular momentum of a nucleus results from the spinning of the
nucleus and
is
It is
quantized in units of
TABLE 52
Stark Splittings
of Rotational Transitions*
Molecule
Molecule
FC1
FBr
BrCl
OCS
HCN NO
s
NH,
PH,
*
NF, CHF, CH 8F
CH
C1
CH,Br CH,I
CH CCH
3
B5H9
From W. Gordy, W. V. Smith, and R. F. Trambarulo, "Microwave Spectroscopy," John Wiley & Sons, Inc., 1953.
ROTATIONAL SPECTRA
93
h/2w, and,
if
the nuclearspin
quantum number
is
designated by
/,
the
spin angular
momentum
1)
Vl(I
where I
0, %, 1, f
If there is no coupling, i.e., interaction between the orientation of the nucleus and that of the molecule, the molecule will rotate and leave the spinning nuclei unchanged in orientation. In such a case the energy of a given molecular rotation state, designated by J, would be unaffected
by the nuclear
spin
/.
If,
is
an energy
of inter
action the energy of the system will depend on the orientation of the nuclear spin relative to that of the molecular rotation. This dependence
momentum of the system. This is usually denoted by F, and the total angular momentum of the system is then y/F(F +1) (h/2ir). A molecuFIG. 54 Dakin,
is
The Stark
splitting
of the J
W. E Good, and
* 2 absorption line of OCS. [From T. W. 560 (1946).] The line for no field
centered at about 24,320 megacycles/sec, and the two markers on each curve are spaced 6 megacycles/sec apart.
No
electric field
750 volts/cm
1,070 volte/cm
Frequency
94
various values of
according to
1,
F = J+
I,
J+I
...,//
(11)
with the provision that the total angular momentum cannot be negative and, therefore, that the J I type terms are not always realized for
states with low
J numbers.
The
splittings of the
from a nuclear spin of f are illustrated schematically in Fig. 55. Something must be said about the source of the interaction between the orientation of the molecule and that of the nuclear spin. For almost all molecules, the exceptions being odd molecules such as NO, this
interaction occurs between the electric field that the molecule exerts
at the spinning nucleus
(All nuclei lack dipole
and the quadrupole moment of the nucleus. moments. Those with / greater than ^, however, have a charge asymmetry that gives them quadrupole moments.) It is,
of course, the directional
asymmetry
is
now
important.
Although
s orbits,
bring
their electrons close to the nucleus, they are ineffective in orienting the
effective
orbits.
and no
directional effect
Again, however, a completed p shell has spherical symmetry, would be imposed on the nucleus. Some inter
of coupling,
The hyperflne
spin
/
splittings (schematic)
a nuclear
s.
F
J
^h^^h
3/2
7/2
5/2
3/2
1/2
ROTATIONAL SPECTRA
for a given nucleus with a given quadrupole
95
of the
atom
is
more
The
by the coupling
of
J and I
to produce
like that
a resultant
of Fig. 55
and the
AJ = + 1
AF =
0,
(12)
provided by the molecule DCN, in which The energy levels and J = > 1 transition, observed by Simmons, Anderson, and Gordy [Phys. Rev., 77 77 (1950) are shown in Fig. 56. In summary: any molecule containing a nucleus with a spin greater than will, if the nucleus is embedded in an asymmetric electric field of the molecule, show such hyperfine structure due to nuclearspin
simple illustration
is
14
interaction.
spectra
by this effect.
Frequency
F=
FIG.
56
The J
>
y= i
1
ab
F=2
F=
l
sorption
and
transitions for
DCN
from
E.
Anderson,
Rev., 77:
77
(1950).]
/=0
F=l
96
*54.
Wave
Functions of
Linear Molecules
It
18,
that the
wave functions
for.
the very
the origin,
ior,
when the wave function was subjected to an inversion through On the basis of this behavi.e., when y was replaced by y.
symmetry
(+
<
operation.
It
was found,
>
+
,
<I>
+,
+>
by electromagnetic
on the basis
transition.
of the plus or
We will now see that plus and minus signs can, in an entirely
This positive and negative character
is
important
weights of
of a
i.e.,
statistical
We now
when
tion
all
diatomic molecule
when
y,
at$
.i
are reversed, as
by the
is
substitu
x, y, z
x,
z. The
effect of this
on ^tota
best deduced
argument,
= Mvfr
(13)
where the subscripts e, v, and r stand for electronic, vibrational, and rotational. We can now investigate the effect of inversion on each factor and then combine these results to see the effect on ^ Mta Inversion of the electronic part of the wave function can be accomi.
plished
by
by 180 deg about an axis perpenand then performing a reflection through rotation axis and passing through the interfirst
Since the
^.
The second
wave function
through the designated plane, and the result of this reflection depends
on the particular wave function that describes the electronic state of the
The nature of the many different electronic waye functions that occur in the ground and excited states of diatomic molecules will be considered in some detail in Chap. 10. For the present it is enough to
molecule.
ROTATIONAL SPECTRA
97
concern ourselves with the electronic wave functions that occur in the ground state of almost all diatomic and linear molecules that have even
numbers
of electrons.
This
common
groundstate function
is
positive
both above and below any plane passing through the internuclear axis. Electronic functions that are symmetric with respect to such planes are labeled with a plus sign, and one finds that most groundstate electronic
wave functions
fact, are
designed as 2+ states.
will be discussed in
Chap.
10.
Most groundstate wave functions, in The basis for the use of the letter 2 For these often encountered 2+ states,
<p e
therefore,
\f> e
we conclude that an
inversion of
unchanged.
\j/
The vibrational component v of the total wave function, depends, shown in Sec. 24, on the magnitude of the internuclear distance. It follows that fa will also be unaffected by an inversion through the origin since this operation leaves the magnitude of the internuclear distance
as
unchanged.
sidered.
,
The remaining factor fa, discussed in Sec. 51, must now be conThe polar coordinate equivalent to the inversion implied by x V> z * ~ x V, 2 is obtained by replacing r, 6, and by r, r 6, and * + The effect of this inversion on fa can be seen either analytically by this replacement in the expressions for fa given in Table 51 or diagrammatically from the wave functions depicted in Fig. 51. On
>
<t>
<j>.
of
fa.
and
reflection through
After rotation
98
manner dictated by fn
as
shown
>
in Fig. 58.
An immediate
(+
i
>
result of this
assignment
+
,
<(>
+,
with electromagnetic radiation in the same way as illustrated for the This result can be recognized to be
detailed analysis
wave
We now
will
proceed to another important type of symmetry make use of the plus and minus assignments
obtained above.
*Exercise 55. Deduce that the interaction of a molecular dipole with electromagnetic radiation can lead only to transitions of the type
*55.
molecule with identical nuclei, or a linear molecule with identical nuclei, such as CO2 or HC=CH. We are concerned now with the effect of an
interchange of identical nuclei on the wave function of the molecule. This feature, which must be considered whenever a system contains like
particles, is
of electrons.
Mention
two electrons
of the
Behavior of ^, otill
on inversion
FIG. 58
S+
ground electronic
state.
ROTATIONAL SPECTRA
99
helium atom
parallel
nuclei of molecules.
For the helium atom, or any atom, the total wave function contains no vibrational and rotational factors and might be written as
</w =
+.
(14)
Furthermore, one can write a suitable approximate expression for ^, atom by regarding each electron as behaving according
to Is hydrogenlike
nuclear change.
**,*.
*.
=
is
(15) of the
This function
trons;
i.e.,
clearly
two
elec
ls(l)ls(2)
atom has lacked the important wave function given behavior of the electrons, and one should
The
electronic
write the
tfWl
lM'.pia
(16)
Each
quantum number
and
momentum associated
say by the symbol
a,
by the symbol
p,
one
as
+

a(2)/J(l) a(2)/S(l)
all
a(l)0(2)
These have
will
To
are
can be written by
** =
l(l)l(2)[a(l)0(2)
this
(2)/8(l)]
(17)
One deduces by
means the
by the
100
usual form of the Pauli exclusion principle, that the electrons of the
its
ground
state,
way the
total
must have opposite spins. wave function for a molecule must behave, nuclei, in a manner dictated by the nature
It
any particle, is the index which determines whether the wave function must be unchanged, i.e., symmetric, or must be changed in sign, i.e., antisymmetric, with respect to an exchange of identical particles. If the spin quantum number of the particle is half integral, as is that of the electron, the wave function must change sign; whereas if the spin quantum number is zero or integral, the wave function must remain unchanged. Particles of the first type, electrons and protons are the most often encountered examples, are said to follow FermiDirac statistics;
andH
(with
lyzed.
The effect of an interchange of like nuclei on ^toU1 will now be anaThen the nuclear spin, dealt with in another connection in Sec. 53, will be introduced in a way so that the complete wave function behaves in a manner suitable to the statistics followed by the nuclei.
It is informative to analyze the effect of
an interchange of identical
this
by imagining
all
exchange to
through the origin, and then (2) of the inversion of the electrons back through the origin. The first step of this process is nothing more than
the symmetry operation treated in the previous section.
We
therefore
on the total wave function, for 2+ states, is plus or minus depending on whether J is even or odd. The second step of the process has an effect that depends only V>n the electronic wave
already
know
that
its effect
function.
Some
electronic
wave
These symmetric electronic which constitute the most often encountered ground states, are labeled. with a g (for the German gerade). Those electronic states which are antisymmetric with respect to inversion through the center of symmetry are labeled with aw (for ungerade). (Note that electronic functions only have g or u properties when there is a center of symmetry as there is in H 2 CO2, and so forth. The property plus and minus assigned to electronic wave functions in the previous section depends on
states,
,
reflection
through a plane containing the molecular axis. Such behavior can be considered even for molecules like HC1, NaCl, and so forth.) The net effect of the twostep process is, if the electronic state is
ROTATIONAL SPECTRA
of the g type, to leave the total of
101
J and
to change
its
sign for
wave function unchanged for even values odd values of J. For u states this conis
clusion is reversed.
equivalent to the
exchange of the identical nuclei, we have found the behavior of the total wave function, exclusive of the effect of nuclear spin, as a result of
this exchange.
this
Symmetric or antisymmetric behavior with regard to by an s or an a. For molecules, such as O u C0 16 that have identical nuclei with zero spin, the above treatment is complete; i.e., no spin function is
exchange
is
indicated
with zero
J can
exist.
The
should show, as illustrated in Fig. 59, only the states with even values of
The absence
of the
odd
be observed in
absorption
like
rise to rotational
nuclei.
The
/
statistical
is
shown.
In (a)
0, in (b)
they have
if.
5
$
A U
.a
ra
.
>
%
.3 tu
/
(5 a)
5i
y
5 a
85
ft
Ortho
f
Para
(3
a)
3 a
ft
0rtho
2
(1
2
1
ft
Para
a)
3
1
ft
ft
"0
Ortho Para
16
CO
16
type
H2
type
(a)
(b)
102
spectra. spectra,
Raman
not be discussed here, confirm the absence of the odd /levels for such molecules. Furthermore, the absence of these levels
which
be noticed in rotationvibration spectra that will be studied in Chap. 7. Let us now consider molecules, such as 2 and H H, that have like nuclei with spin quantum number ^. (The C 12 nuclei of
will
C=C
for the
/3/3,
As
two and
and one antisymmetric function a/3 /3a can be written. Furthermore, nuclei with a spin quantum number of ^ follow FermiDirac statistics that require a total wave function which is antisymmetric with
/3a
odd values
coupling
\f/
of
toU1
J can be brought
by suitably
Thus one
even, as
*.lMv(a/3
/3a)
and
odd, as
symmetry
whereas only one spin function makes the total wave function antisymmetric when J is even, the odd J levels have a statistical weight due to the spin function of 3 while the even J levels have a
levels
odd J
weight of
1.
have an additional multiplicity factor of 3 while this factor is only 1 for even J levels. Again this alternation in multiplicities, which leads to an alternation in populations, illustrated
levels
odd J
HC=CH
is
components
of rotationvibration absorption
bands
observed.
recognize that the analysis given above has led us to
One should
parallel
spins.
]\
recognize the ortho states of RYlike molecules, which are those having
][
nuclear
very strong selection rule exists which prohibits, by any mechanism, transitions between s states and a states. Thus ortho and
para states cannot be interconverted, unless the molecules are dissocia< s, > o, One should notice that the selection rule s < ated.
ROTATIONAL SPECTRA
s
< * which applies to homonuclear molecules, and <+ molecule, elimdiatomic any > applies to which + _)_ inates the possibility of pure rotational spectra of diatomic homonuclear
_[_>
a,
103
\
molecules.
and
so forth.
all
levels
symmetry required by the nuclei. with even and odd J values, have different
SYMMETRICTOP MOLECULES
Symmetrictop molecules are defined as those having two equal principal moments of inertia, the third being different from these two.
The unique moment of inertia is generally represented by IAl while the two equal moments of inertia are I B = Ic Most symmetrictop molecules that will be treated belong to this class because of a arrangement of some of the like atoms of the molecule.
symmetric
typical
example
is
plane of the carbon atoms, and the two axes with equal moments of inertia pass through either the carbon atoms at opposite corners of the square
or through the opposite sides of the square.
ides also are symmetrictop molecules.
The
cules will
classical
first
be given so that the quantized angular momentum restricA statetion can be applied to give the allowed rotational energy levels.
FIG. 510
i.e.,
those with
U?*
In
to.
(I 4
< /
(1 A
>
l B
104
ment of the selection rules will then allow the spectral transitions drawn in and a comparison with observed spectra to be made.
56.
to be
As with
can
momentum
moments
e
restrictions.
,
of inertia IA
Ib,
= 
A+A+A
2IA
,
'
ilA^\
+ \Ib<b + %Ic<*c
2IB
'
27,c
as,
where pA Pb, and p c are the angular momenta about the three axes. For a symmetrictop molecule I B = Ic, and this general expression becomes
"&+#. + ft
that the total angular
(")
The energy levels of a quantummechanical symmetrictop system can be obtained from Eq. (19). As for linear molecules, it is assumed
momentum
is
number
J,
is
given by
VJ(J +
The
1)
J =
0, 1, 2,
(20)
correct quantummechanical solution for symmetrictop molecules obtained by further assuming that the component of the angular momentum about the unique axis is quantized and that this quantization
is is
K 27
K==0 X 2
> >
>
>
< 21 >
where the plus and minus values correspond to the possibility of clockwise and anticlockwise rotation about the unique axis. These quantum
restrictions lead to
and
Pi
(22)
+P c
>
= j(j +
i)(Ay_^(Ay
ROTATIONAL SPECTRA
105
and
tJK
(23)
&* 2 cIb
,^ +
1
)
(8^8^r>
and
cm"
It is again
and
defined
by
cm_1
B = iJcT B
A =
s^n
cm_1
with
= BJ(J + J = 0, 1, 2,
.
1)
.
(I
E)K*
0,
(24)
. . .
and
K=
1, 2,
+J
This expression gives the same set of energy levels that would have been obtained if solutions to the Schrodinger equation for a rotating
symmetrictop molecule had been sought. By the application of the appropriate quantum mechanical operators, one would also have found that the quantum number J determines the total angular momentum of
the system while the number
momentum
along the unique axis of the molecule. It will only be mentioned here that Eq. (24) corresponds to the assumption of a rigid molecule and that additional terms must be intro
As
for
linear
molecules
treated in Sec. 35, the shifting of the energy levels due to this effect
The
by a diagram
of the
J and K.
Two
different
moment
of
than I B = Ic are said to be prolate molecules. An exam2 in Eq. (24) For such molecules the coefficient of ple is CH 3 CN. is positive, and for a given J value the higher the value of K, the higher
the energy.
benzene.
_ greater than I B
Molecules that have the unique moment of inertia IA Ic are said to be oblate molecules. An example is
2 is For this class of symmetric tops, the coefficient of negative, and for a given value of J the higher the value of K, the lower
106
the energy.
The
two cases
are
shown
Exercise 56.
inertia.
Given the geometry of the CH 3 C1 molecule in Table 53, and calculate the three principal moments of Also calculate the rotational constants and plot to scale the first
levels.
moment have
moment
molecule.
AJ =
and
0,
+1
AK = AK =
for
Z^
(25)
AJ = +
for
For an absorption experiment, the part of the selection rule that corresponds to an increase in the energy of the system and is appropriate is
AJ = +1
The
AK =
(26)
between different values can be understood from the fact that, for the molecules considered here, rotation about the figure axis contributes
Some Molecular
Molecule
Bond
angle
Bond
distances
CH,F
CH C1 CH Br CH CN
3
8
1100'
CH,C=CH
CHC1,
NH,
*
HNH
&
Sons, Inc.,
CF
CC1
CBr
CC
1.097
CC
s=CH
CC1
NH
1.016
From W. Gordy, W.
John Wiley
'Microwave Spectroscopy,"
f*.
to
in
3 u
IT)
>* o>
J
4
J
4
JJJJ
_o
*
o
E
.
Q.2 c
6 ~
e
>
.
^
Q
8.
o O
E o
3
* IS
IO
^
J:
>
a* c
T
> o
P>
OS
E o
1^
SI
107
108
K(AK = 0)
\i
*i
l
12
0v\
0v\l/
l2
A/
0
z
*j
I
FIG. 512
l_
transition absorptions
Raman Spectra,"
D.
Inc.,
of
With the
Eq.
v
selection rule
AJ =
1
+1 and the
energylevel expression of
= 2B(J +
for
1)
is
cm
(27)
was found
a linear molecule.
expression
v
= 2B(J
1)
 2D KJ K\J +
If
1)
4Dj(J
l) 3
(28)
between
linear
and symmetrictop
spectra.
The
J =
> 9
transition of
CF CCH
3
are
shown
in Fig. 13.
The
alterna
FIG. 513
distortion.
=
is
* 9
transition of
CF 3 CCH showing
[From
(1951).]
W.
f.
Anderson,
Trambarulo,
Sheridan, and
W. Gordy,
58
ROTATIONAL SPECTRA
109
components
is
58. Results
about the two equal moments of inertia about the axes of the molecule perpendicular to the figure axis. This one determined quantity is, of
course, insufficient for the determination of the
Again
it is
make use
of
As we will see, however, such a procedure requires the assumption that bond lengths and angles are independent of isotopic substitution; while this would undoubtedly be true to a very good approximation if the atoms were at their equilibrium positions, it introduces some uncertainty when data for the v = states are used. Another procedure is to make use of
different isotopic species to obtain further momentofinertia data.
on the internuclear distances between the heavy atoms and to supplement these data with the momehtof inertia result from the rotational spectrum.
In this
fix
trum
of
a given molecule,
many structures have been determined with conof these structures are listed in Table 53.
siderable accuracy.
Some
ASYMMETRIC MOLECULES
moments
of inertia is
known
as an
asymmetrictop molecule.
with
much more difficulty than was encountered for linear and symmetricThe Energy Levels of an Asymmetrictop Molecule
top molecules.
59.
The rotational energy of an asymmetric system can be expressed by the general, classical formula
Va 27 A
+ ^ #: + #.
P%
, i
21B
Vl 21 c
(29)
110
momentum,
ignoring nuclearspin
angular
momentum,
is
Total angular
momentum = y/J(J
1)
5
(30)
momentum
is
is
quantized; therefore, no
J there
will
be 2 J
1 states.
We
by the
fol
lowing statement.
characterized
states
+J, can be expected only to 0, +1, 2, shift the energy levels and would not eliminate any of the allowed states. This "adiabatic" argument shows that, even for an asymmetrictop moleA difficulty cule, the 2/ + 1 states will still exist for each value of J.
by
. .
K=
no quantized component of this total angular momentum; i.e., K is not a "good" quantum number for an asymmetrictop molecule. Solution of the Schrodinger equation for an asymmetrictop molecule has been accomplished, although the problem is one of some difficulty, and for each value of J it is found that there are 2J + 1 solution functhere
is
tions,
each with
are
track
own energy. Since these 2 J + 1 solutions for a given not characterized by quantum numbers, it is customary to keep This index t is of them by adding a subscript to the J value.
its
J for the
is
+J for
any but the lowest few energy levels of an asymmetrictop molecule. The nature of the energy pattern can, however, be illustrated by a diagram of the type shown in Fig. 514. The energylevel pattern for an oblate symmetrictop molecule, for example, with A = B = 3 and C = 1, is drawn at the left of the diagram, and the corresponding symmetrictop diagram for the prolate symmetrictop molecule, for example, with A = 3 and B = C = 1,
closed general expression
available for
No
axis unique.)
ically connect the energy levels of the symmetrictop patterns to show what would happen if the moment of inertia along the B axis were grad
ROTATIONAL SPECTRA
111
1.
In this way, the interconnecting lines of Fig. 514 are drawn. a subscript to each
The J
value of any line remains unchanged, and the index t can be entered as
value as shown.
The
One can
is
related to the
FIG. 514
rotors.
correlation
diagram
illustrating the
(From
W. Gordy, W.
Inc.,
V. Smith,
and
R. F.
New
York, 1953.)
Prolate
symmetric top
Asymmetric top
symmetric top
112
cules according to
T
Kprol.te
KobUte
(31)
With
t
as J, or with the
notation
is 3i, 3
K notation as Jk .k Thus a level 3_2 with the with the K notation. Both types of notation may be
. , prolate'
encountered.
of
asymmetrictop molecules,
k
it
is
A convenient
K
quantity
is
the
asymmetry parameter
defined as
= 2[BUA +
C)]
C
C
are the rotational constants
where A, B, and
A = 5JV
One can
cm
etc.
(33)
Ia>
Ia
as
Ib
Ic
C, k
and therefore
A <B=
C =
<
Ib
=
3,
tops, k lies
C, k
= 1.
For
all
asymmetric
A =
B =
0.
The
by B.
S.
Ray
[Z.
Physik,
[J.
W. King, R. M.
27 (1943)] for the energy levels of some of the lower J states of asymmetric molecules are listed in Table 54. For states with higher J values, energies have been tabulated for
Chem. Phys., 11
Chem. Phys., 11
Exercise 57.
and Structure
Results for
Asymmetrictop Molecules
The
selection rule
is
AJ =
0,
molecules,
Now, even
in absorp
tion spectroscopy,
since, as Fig. 514
necessary to retain
all
ROTATIONAL SPECTRA
in the order of J;
i.e.,
113
an energy
level
J may
occur
These depend
on the components
of the dipole
moment of the molecule along the The selection rules themselves, and
it is adequate here merely to indicate that they are treated in ref. 2. The complexity of the energylevel diagram of an asymmetric top leads, with the selection rules for induced transitions, to a corresponding complexity in the observed rotational spectrum. The assignment of each of the observed lines to the energy levels involved in the transition is now
a problem of some
splitting observed
lines
difficulty. The most helpful aid in when a Stark field is applied. The
this
work
is
the
splittings of the
the
J and
and the relative intensities of the components are t numbers involved in the transition.
difficulties
characteristic of
In spite of the
Some Closed
Asym
Jku
i)K<_+i)
Energy
ero t.
Ooo
lio
ln
loi
A +B A +C B +C
'
2M
2*i 2,i
2
2o2
C) s
(A
C)(A
B)
C)
(A
C)(A
B)
C) C) C)
3 30
3 31
32, 3 S2
3i 2
3i 3o.
4 4 4
4 2S
4,
5A 5A
10A
4m
5A 5A
+ 48 + iC + 5B + 2C  2 V 4(A  B)* + (A  C)(fi  C) + 2B + bC  2 VA(A  C)  (A  B)(B  C) + 5B + 5C  2 Vi(B  C)* + (A  B)(A  C) +5B +5C +2 V4 (B  C) + 9(A  C)(A  B) + 10B + 5C + 2 V4(A  C)'  9(A  B){B  C) + 5B + IOC + 2 V4(A  B)' + 9(A  C)(B  C + 5B + 5C  2 V4 (B  C) + 9(A  C)(A  B) + 10B + 5C  2 V4(A ^ C)i  9(A  B)(B  C) + 5B + IOC  2 V4(A  B) + 9(A  C)(B  C)
1 ) !
114
Some Molecular
Asym
metrictop Molecules*
Molecule
Bond
angle
Bond
distance
S0 2
0, CH2CI2
0S0
00 '0
HCH
C1CH
SO OO'
CH2
\/
CH2
HCH
COC
0S0 FSF
6124'
S0 2 F 2
12938' 9247'
1.433 1.278 CH 1.068 CC1 1.772 CH 1.082 CC 1.472 CO 1.436 SO 1.370 SF 1.570
* From W. Gordy, W. V. Smith, and R. F. Trambamlo, "Microwave Spectroscopy," John Wiley & Sons, Inc., New York, 1953.
energy
studied and the observed transitions identified with the participating When this is done, one can use the equations of Table 54 levels.
or the tables of King, Hainer,
moments
These
when supplemented by
Some
of the results that have been obtained from such studies are shown in Table 55.
PRINCIPAL REFERENCES
1.
2.
Gordy, W.,
Herzberg,
John Wiley
3.
W. V. Smith, and R. F. Trambarulo: "Microwave Spectroscopy," & Sons, Inc., New York, 1953. G.: "Infrared and Raman Spectra," D. Van Nostrand Company,
THE VIBRATIONS OF
POLYATOMIC MOLECULES
An
now be presented. This theodevelopment provides the background for an understanding of the
liquids containing polyatomic molecules.
absorption spectrum in the infrared region, like that of Fig. 21, of solutions
and pure
In the follow
and rotation
of molecules will be
and the absorption spectra of gases, which show the effect and rotational energies, will be studied.
If a molecule containing n atoms is imagined to have these atoms held together by extremely weak bonds, the motions of the system might
best be described in terms of the motion of the n, nearly independent individual atoms. If three cartesian coordinates are used to describe the position and motion of each atom, there will be a total of 3n such
coordinates required for a description of the set of the n atoms. Each of these 3n coordinates represents a degree of freedom of the system in that any arbitrary displacement and velocity can be given along each
these 3w, that
Any additional displacement or velocity, beyond imposed on an atom, or on the molecule, could be described in terms of the 3w cartesian coordinates. For actual molecules the 3n cartesian coordinates are not, in fact, very convenient. One can recognize that if the bonding of the hypothetical molecule with very weak bonds were to be gradually strengthof these coordinates.
is
115
116
ened,
would become increasingly important to recognize the existence than to treat the system as consisting of n rather
particles.
independent
One
likes, for
mass
If
ening of the bonds between the atoms as one goes from a set of inde
pendent atoms to the rather firmly held set that constitutes a molecule, one will see that none of the 3w degrees of freedom is destroyed. The
degrees of freedom are merely reclassified.
translational
It follows that
if
three
and three rotational degrees of freedom are recognized, there will be left a total of 3n 6 degrees of freedom which must be accounted Displacements and velocities for by internal coordinates of the system. in accordance with these 3n 6 coordinates constitute vibrations of the
molecule.
If
the molecule
is linear;
the two axes that can be drawn perpendicular to the molecular axis.
For such molecules, three overall translations and two overall rotations are subtracted from the total of 3n degrees of freedom, and there remain
3m
The number of internal degrees of freedom of a molecule corresponds to the number of ways in which the atoms of the molecule can be given independent displacements and velocities relative to one another. They are, as will be shown in the following section, the number of vibrations
of the molecule.
It is
now
necessary to see
if
these 3n
molecules, 3n
62.
collection of
many mass
initial
units interconnected
by
springs can be
expected to undergo an
motions, or vibrations,
depending on what
system.
The
there are 3n
6 (or 3n
is,
5)
For any
molecule there
The nature
of
by a
If
held
by
THE VIBRATIONS
OF POLYATOMIC MOLECULES
117
x and y coordinates are set up as indicated, the motion of the particle, can be deduced from the potential and
kinetic energies
where the springs have been assumed to obey Hooke's law and to have and kv [It should be noticed that the spring system, for small displacements, is such that the restoring force in the x direction
force constants k x
.
arises only
from a displacement
in the
x direction and,
similarly, forces in
the y direction only from y displacements. One can see that the potentialenergy expression of Eq. (1) leads to this result by forming
J'
= 
(j^r
\*v).
~ k**
and
/.
Kv]
can
The motion
of the particle
now
(3)
mx
This
is
fcjX
(4)
the
now
familiar differential
FIG. 61
twodimensional, oneparticle
spring system.
118
= Ax
sin (2nvJ
<p x)
(5)
where
'
\P
(6)
my
+ kyy = +
(7)
= Ay
sin (2wv y t
<p v )
(8)
where
*v
*/^ 2*
0)
displacements along the x or y axis will, therefore, lead to Displacement in any other simple sinusoidal vibrations along this axis. that can be interpreted in motion direction will lead to a complicated
Initial
terms of sinusoidal components in the x and y directions; i.e., Eqs. (5) and (8) will simultaneously apply, and the motion is described when the appropriate values of A x and A v for the displacement are used.
of the particle to
be most
system along a normal coordinate consists of simple harmonic motion, and such motion is said to be a normal vibration or
Motion
of the
normMl mode.
Similar normal coordinates and normal vibrations will exist for more complicated vibrating systems. In such cases a normal coordinate
will, in general, consist of
one atom of the system. be a complicated combination of atomic displacements. In terms of this coordinate, however, the vibrational motion of the system will be simply described, and a displacement of the system according to the normal coordinate mil lead to a simple motion in which all the particles move in phase
with the same frequency and, if Hooke's law is applicable, will execute
the displacement coordinates of more than The normal coordinate will, therefore, often
(For some systems, as we will see, it will be necessary to modify this description of normal coordinates so that it is lead stated that displacement according to the normal coordinate will
simple harmonic motion.
t0
all
Calculate the classical natural frequencies of this system. showing, side by side, the allowed energies for the two normal modes treated quantum mechanically. What would be the wave numbers of the radiation absorbed in the fundamental transi(a)
(b)
Draw a diagram
tions of this
system?
the
not
advance the directions along which the springs lay and, therefore, did know the convenient directions in which to choose coordinates. The
simple calculation that is necessary will, in fact, anticipate the problems that will arise with molecular systems where one generally does not initially know what coordinates are the normal coordinates and, therefore,
will lead to
Let us suppose that the spring system of Fig. 61 has been turned through an angle as shown in Fig. 62. The axes relative to this orientation of the system are labeled x'
difference
and
y'
as in Fig. 62.
The
essential
between the axis choice of Fig. 61 and that of Fig. 62 can be recognized by considering the restoring force that would act for displacements along the coordinate axes. In Fig. 61 it is clear that displacement
FIG. 62
Fig. 61
described by an
such
as might be used
were not
,,
known.
9X
]20
force acting along along the x axis, or the y axis, results in a restoring the basis for the was This origin. that axis and directed toward the
form of the potential written in Eq. (1). the coordiFor the coordinate system of Fig. 62, displacement along
lead to restoring forces nate axes will not, as the force vectors suggest, function has the potentialenergy the that along these axis. It follows
form
u = %KWY + KWKv') +
iW)
(10)
the restoring forces This potential expression can be seen to lead to one has Thus 62. Fig. of orientation expected for the spring
(id
ments in both in advance, will where the normal coordinate directions are not recognized is not just the sum of squared lead to a potentialenergy expression which between the coordinates. products cross addition, terms but contains, in
vibrations of this oneparticle Let us proceed now to study the The potential is written in 62. Fig. of system, using the coordinates the kinetic energy orthogonal, still are Eq. (10), and since the coordinates
is
therefore, from displacerestoring force in the a? direction can result, coordinates, the x' and y' directions. Thus, a selection of
t =
im(x')*
+ iMy'y
x'
(12)
coordinate
now
gives,
ma?
k'j!
y'
 Ktf =
coordinate,
(13)
my'
KX
Kv'
(14)
Although these equations are clearly less and Eq. (7), we can again look for vibrationtype
frequency of vibration
x'
is v,
(4)
where the
= =
+ +
9)
and
y'
sin A' y
(2irvi
<p)
121
and
y'
4**p*mA' m
k' x x A'
k'^A,
=
(16)
and
4**,*mA',
k' x xv A'
k' A' y
For these equalities to hold, for other than the trivial solution with = 0, the determinant of the coefficients of the amplitudes A' x A' y
must be
zero;
i.e.,
4rrVm k' xy
k'
k'.
4tVto 
k' y
(17)
(4rVm The
k' x )(4w* v *m
k' ) y
2
(k' xv
Y =
(18)
(*:
/
K) +
kk k' y y + 404)?
by Eq. (19) can be substituted into Eq. (16); the appropriate minors of Eq. (17) can be calculated, and values for the ratio of A' can be obtained for each vibration x to A' y frequency.
Finally, the roots given
or, alternatively,
Exercise 62. When the spring and particle system of Exercise 61 is rotated counterclockwise by 30 deg with respect to the axes, now labeled
x'
and
y',
is
V =
(a)
10
)(z')
+ VI X
lW{x'){y')
+ (1.75 X
10 B )(y') 2
Calculate the natural frequencies of the system, and see that the in Exercise 61. (b) Calculate the relative values of A' and A' for each vibration, and x y see that one can deduce, from the given potential function, the directions in which the particle moves in each vibration.
This rather detailed treatment of a very simple system will later be recognized as an illustration of the procedure that .is necessary when the
relation treated.
between the force constants and vibrations of a molecule is The immediate purpose of the example is to illustrate that
122
there
Furthermore these coordinates are and potential energies to be written even if these convenient coordinates Finally, sunt squared terms. as the of the problem known, of can be carried through initially solution are not
with any other set of coordinates, and the normal coordinates can then be deduced from the amplitudes that are obtained for the natural, or
normal, vibrations of the system.
63.
Polyatomic Molecules
the
Schrodinger
equation
have been
The equation
can, however,
be written for n
as
cartesian coordinates.
In this
way
written
*(3 + 3 + f) +l "*
where the function ^
will involve
>*=<*
As One
<2 >
the 3n coordinates.
in the classical
can, as in the
motion of the center of mass of the system and the three (or two for a linear molecule) that describe the rotation of the system about the The derivation that shows how this principal momentofinertia axes.
separation of external from internal coordinates
is
can be found in many texts on quantum mechanics, as, for example, "Introduction to Quantum Mechanics," by L. Pauling and E. B. Wilson (McGrawHill Book Company, Inc., New York, 1935).
be given here.
It
Let us
now proceed
when
it
is
Furthermore we
by Q
of the molecule.
In general one
is
not initially able to describe these normal coordinates atoms of the molecule. We know,
however, from the simple example of the preceding section the important fact that normal coordinates are such that both the kinetic and potential energies of a system are expressed by the sum of terms each involving
the square of a normal coordinate.
123
The
correct
form
6 (or 3n
5)
normal coordinates can be deduced from the fact that the kineticenergy operator for a coordinate Q, is given by an expression of the type
h2 a 2 &r 2 dQ?
in the
denominator of this
The operator
itself.
tion
is
terms of the normal coordinates, the kinetic energy a function of squared terms, one can write
Since, in
3n6
h2
Y*
d 2 J/
(21)
will, in general,
be a function of the 3n
This manydimensional equation is greatly simplified because of the fact that, in terms of normal coordinates, not only is the kinetic energy a sum of squared terms, but so also is the potential energy. The
UiQtQt
Q 3n _ e ) = i^Q 2
3n6
+ iXzQ +
2
+ iA _,Qn^
8
=i X
where the
molecule.
X's are coefficients that
X<
&
( 22 )
X H+ X
(5
* =
**
(23)
It is profitable to try to separate this equation into 3w 6 equations, each involving only one of the normal coordinates. We write
* = *l(Ql)*l(Q0
or
*3,(<236)
(24)
124
and
When
this is
equation
or
(25)
is
The
of the 3n 6 equations like Eq. (25) are, therefore, the harmonic Furthermore, each normal oscillator wave functions listed in Sec. 24. coordinate Q will lead to a set of energy levels with a constant spacing,
t
such as shown for the onedimensional case in Fig. 24. The important result has been obtained that, since normal coordinates allow both the kinetic and potential energy to be written as the
sums
quantummechanical problem
(cf .
the classical
solution at the beginning of the previous section) is separable in terms of molecule containing n atoms will have, therefore, these coordinates.
3n
6 (or 3n
responding to one of the classical normal vibrations of the system. Since the wave functions written in terms of normal coordinates
as those discussed in Sec. 24, the selection rules for transitions between the vibrational states for each normal coordinate are are the
same
Ai>
= 1 = +1
(26)
27 >
again obtained.
We
(We
symmetric molecules
some
The
energylevel diagrams
in Fig. 63.
and
are
shown schematically
perhaps should be pointed out that in general we do not know the normal coordinates of a molecule. For some of the simpler molecules they have been deduced, but their deduction is often rather difficult. The previous derivation of the separation of the vibrational problem does
not, however, require us to be able to describe the
It is sufficient to
normal coordinates.
know
and
125
is
to be treated in terms of
3n
6 energylevel patterns.
d4.
Normal coordinates
molecule.
all, of the atoms of the some symmetry, as many do, a great The consequences of symmetry in molecular simplification occurs. spectroscopy are, in fact, widespread and profound. One way in which symmetry enters into treatments of molecular systems will here be illustrated by a discussion of the nature of the normal coordinates of a
When
symmetric molecule.
symmetric
Chap.
8.
Here
it
will
be enough to consider
the molecule in
a plane of symmetry;
i.e.,
its
The energylevel patterns and schematic representations of the corresponding and a schematic infrared absorption spectrum of HsO.
A? = 3,756 cm 1
A =3,652 em
it
l,54Scm
600 cm
126
equilibrium configuration
identical
on both
It is
customary to
such a plane an element of symmetry. The axis of the molecule of COj is another such symmetry element
call
of the molecule.
atoms
of a molecule
from
These
To deal with the s in Fig. 64. symmetry elements, one introduces Thus the symmetry operation corthe idea of a symmetry operation. responding to the plane of symmetry is a reflection through the plane.
placement of an oxygen atom of
relation of such displacements to
CO
manner shown.
It should
The symmetry
symmetry
will
is
also
shown
in Fig. 64.
be kept
by symmetry operations; only the displacement vectors will undergo the symmetry operation. That symmetry and normal vibrations are related can be readily If one were illustrated by reference to the spring system of Fig, 65.
unaltered
its
natural or normal
modes
of vibration,
In this simple example it is obvious, particularly if one has a model to work with, that the coordinates along which the system must be distorted in order for the particles to vibrate in phase and with the same frequency are either symmetric or antisymmetric with respect to the plane of symmetry. A similar conclusion can also be drawn for the less easily visualized normal coordinates of molecular systems.
Fig. 65fc,
FIG. 64
axis of symmetry.
Symmetry
operations corresponding to these elements transform the solid arrows into the dashed
arrows.
Plane of symmetry
Axis of
symmetry
127
To do this, it is first necessary to point out that both the kinetic and potential energy of a molecule must be unaltered by a symmetry operation. If a symmetry operation is performed on a distorted molecule, which has, therefore, some higher potential energy than the equilibrium configuration, the distorted molecule that
is
obtained by the
symmetry operation
distorted one.
will
is
This
have the same potential energy as the original illustrated in Fig. 66a. In a similar way, if a
its
atoms, a symmetry
in Fig. 66,
This
is
apparent
where
the velocities of the atoms are represented vectorially and the the magnitude of the velocities of atoms of given masses.
symmetry
It follows
operation changes the directions of these in space but does not affect
it
molecules.
^Q\
iX,QJ
+ iQ\ +
&tQi
^"3B _6y Sn _e
(28)
Now,
since the normal coordinates represent the displacements of the atoms during a vibration, they can be represented by displacement
FIG. 65
and
(b)
antisymmetric
initial
LwwB/SAA/1 IaA/S/B^VW
(a)
(h)
128
Distorted
J~
position
Reflection
7* Diane of
symmetry
through
fnj
Reflection
through
plane of
symmetry
CM
FIG. 66
kinetic
Illustration that
energy of a molecule.
seen that for the energy to remain constant, in the general case
all
where
Thus,
X<
are different,
is
performed,
of Eq. (28)
is
unchanged
as a result of a
symmetry operation
(29)
Q* Q>
This important conclusion
or
is
a symmetry operation.
With
this result
one can, for example, immediately represent two of the normal coordinates of the
67,
CO
molecule.
to
draw arrows,
as in Fig.
no
FIG. 67
COa
in
two normal
12? left
unchanged or
change of
when a symmetry
For simple molecules with a high degree of is performed. symmetry, as for C0 2 one can often write down immediately the form In general, however, the symmetry properof the normal coordinates. ties of a molecule can be used to classify the normal coordinates accordoperation
,
the various
symmetry operations
of the molecule.
is
In later chapters
we
will sec
The
all
This the normal coordinates have different values of X in Eq. (28). supposition corresponds to cases in which all the normal vibrations
have different frequencies. The bending vibrations of two perpendicular planes, as shown in Fig. 68, provide an The illustration of normal coordinates that have equal values of X. frequency expected for each vibration is therefore identical. Such vibrations are said to be degenerate, and in this case, since 2 degrees of freedom
of the molecule
COs
in the
When such degeneracy occurs, the requirement that the energy remain unchanged during a symmetry operation does not lead, accordIf the normal coordiing to Eq. (28), to the restriction that Qi > Qi.
nates of the degenerate vibration are Qi and Q%, one has
*
= IQ\
+ i^Ql + iQl +
of
i^iQl
(30)
coefficients
Xi.
Rearrangement
<
= HQt
QI)
+ 1MQ1 + +
+
(3i)
Now
long as the
FIG. 08
the energy remains constant, as far as Qi and Q$ are concerned, as symmetry operation does not change the value of Q\ Q.
The two components of the doubly degenerate bending vibration of COs.
130
FIG. 69
Q\
Q'z
=Q (cos9) + e2 (sinfl)
1
the
Within this
restriction, it is
the transformations
Qi 
aQ x
bQ t
(32)
and
An
C0
about
its axis
In summary, the behavior of normal coordinates with symmetry operations can be stated as
1. For nondegenerate vibrations, the normal coordinates remain unchanged or change sign. 2. For degenerate vibrations, each normal coordinate of the set
nates of the
can be transformed, by the operation, into combinations of the coordiset, subject to a restriction imposed by the particular sym
metry operation.
Exercise 63. Draw, to the extent that one can on the basis of symmetry and zero translation and rotation, arrows showing the relative displacements of the atoms of the linear molecule CS2 and the bent molecule H2S in the normal vibrations of each molecule.
PRINCIPAL REFERENCES
1.
Raman
Spectra," chap.
2,
D. Van Nostrand
Company,
2.
Wilson, E. B.,
New York,
1955.
ROTATIONVIBRATION SPECTRA
When
by a pure
liquid or
by a material
in solution
is measured, welldefined regions of absorption which can, to v  1 transitions in the the most part, be attributed to the v = for Typical liquidphase observed. are patterns energy various vibrational
shown
in Figs. 21
it
mode
The
is
The
structure
of such absorption
bands can be attributed to changes in the rotational energy of the molecule accompanying the vibrational transition. In the liquid phase no welldefined rotational energy levels exist, and rotational structure is not observed on a vibrational absorption band. We will now investigate in some detail the nature of rotationvibration bands, and we will see that molecularstructure information can be
deduced from an analysis of the structure of such bands.
Furthermore,
the nature of the rotational structure of a rotationvibration absorption band will be seen to reveal much about the type of vibration that is
occurring,
be of great aid when we attempt to match up the observed vibrational absorption bands with the normal
and
The
3
,
UOtSStlUSUBJ* tU&iJfyj
S2 u.
133
134
and
symmetric top,
will
The
complexities that
arise in the rotational energylevel pattern of asymmetrictop molecules lead to corresponding complexities in their rotationvibration bands.
These
will
DIATOMIC MOLECULES
71. Selection Rules
and Transitions
Oscillator
Model
and vibrational
and
The
remain applicable when both types of energy are changed in a given transition. For absorption spectra, as before, the selection rule Ay = +1 is appropriate and the fundamental
transitions, given in Chaps. 2
transition,
from
as
to v
1,
is
The
selection
rule for
J was given
are important.
Thus the
Av
band
are
(1)
= +1
AJ = 1
NO that
odd
electron.
axis,
momentum
molecular
and
AJ
transitions to occur.)
These
rules,
The
simplest,
and
fairly satisfactory,
With
this approximation,
one writes
(2)
treated earlier,
i.e.,
the anharmonic
rotor, could
2
to terms involving
are,
+ )
and
[J (J
however, of
will
less
term that
ROTATIONVIBRATION SPECTRA
It is
135
\/2t
Wm by
*
v
and l/2rc y/kh* by the symbol u>. With and the selection
At for the
transitions as
i.e.,
For AJ
;
= +1,
5>
S,
= =
(3)
For AJ
i>
1,
> J
l)(/)
1,
= &+ = w 
5[(J
 J (J +
=
1)]
. . .
2B(J)
where J
1, 2,
(4)
is
One should note that in these expressions the value to be inserted for J the rotational quantum number for the lower vibrational state. These transitions, and the resulting absorption lines, are best shown
on a diagram such as that of
Fig. 72.
There
it is
clear, as
the above
by the constant amount 25, on the highfrequency side of the band center, which occurs at v = u, and a corresponding set on the lowfrequency side with a similar constant spacing.
transitions, all of
AJ =
which would have had a frequency <a. the lowfrequency set of lines as the P branch
It is
customary
(For
of the rotation
vibration
side as the
branch.
branch is allowed, some molecules, as we will see, the central AJ = and it is known as the Q branch.) The infrared absorption spectrum of HBr shows the absorption,
given in Fig. 73, that can be attributed to the
v
is,
to v
1 transition.
The
and
It is clear
= 0,J=0tov =
in the
J =
from the
gap band and that this value gives the spacing of the vibraFurthermore, the separation of the tional energy levels of the molecule.
central
components
of the
quantity 25.
From
moment
of inertia
of the molecule can be deduced as they were when the spacing of pure rotational lines was determined from studies in the
136
' '
.i
Energy levels
00
1
"5
10
1
'5
1
a
i&
ii
'8
'5
to
+
i&
ii
+
i&
ii
+
l&
II
00 1%
II
la.
II
i=>
II
i&
II
<
20B
<
<
<
i*
<
l<u
\1l
<1
<
<
12B
6B
IB
1
_
*
2fi
Spectrum <
(P branch) (A branch)
FIG. 72
The
transitions that
in
linear molecule
independent of
Two
features illustrated
Fig. 73
have not
components remain to be investigated and, second, the components are not found to be exactly
relative intensities of the components of bands such as that of can be understood on the basis of the population of the various The approximarotational energy levels of the ground vibrational state. Fig. 73
The
tion can be
made that
o
II
5
S
uojsniusuej) jure Jd
o E
137
138
vibration band are proportional to the populations of the rotational energy levels from which the components originate. As was shown in
Sec. 33, the multiplicity of the
and
it
tion of the
Jth
(2/
level is
Nj =
l)N
e jr ( J + h, i*'"<T
(
5)
The momentofinertia value for the molecule being studied and the temperature of the experiment can be substituted into this expression, and the value of Nj/N can be calculated for various J values. The
intensities of the
components starting from various J values will be Nj/N The absorption band predicted
.
on
this basis,
will
correspond rather
Exercise 71.
and 10 energy
levels of
Calculate the relative populations of the J = 0, 2, 4, 6, 8, HBr at 25C, and compare these results with the
components
of the
and
branches
is
shown
in Fig. 73.
(Much
because of the experimental problems that arise when very sharp absorption lines are measured.)
73.
The energylevel expression of Eq. (2) is based on the assumption that the energy of a molecule can be treated in terms of separate contributions from the rotation of the molecule and the vibration of the
molecule.
The
on
this basis
the spacing of
the components is not constant, can be attributed to coupling between the rotation and the vibration of the molecule. This coupling introduces a cross term in the energy expression for a rotatingvibrating molecule
that involves a term of the type
(v
+ $)J(J +
1).
it
This term
is
usually
depends, since
bond length
r,
(v
1)
(6)
where
quantum number.
One
finds, in fact,
pretty well
ROTATIONVIBRATION SPECTRA
139
represented
by an expression
of the type
(7)
B,
B,
a.(v
+ i)
where B is the rotational term corresponding to the equilibrium bond length and a, is a small, positive constant.
With
this
transition frequencies P
Ae for the
to v
transition as
R branch, J J +
>
vB
= =
i
>
(8)
branch,
vp
J * J
[5x(J
1 1)]
S
= + = ib 
(B 1
(9)
Since the higher energy vibrational state has a greater vibrational amplitude, it will have a larger effective value of r. It follows that
Ii
>
Jo
and that
branches are therefore negative. It is these terms that are primarily responsible for the nonconstant spacing of the components of a rotationvibration band and for the asymmetry of the
expressions for the
B <B P and R
x
The
coefficients of the
J 2 terms
in the
band that
of the
is
73.
on
P branch are at frequencies that are lower than would be expected the basis of 6 = So = B, and as a consequence this branch extends
t
The high J components of the frequencies than would be lower somewhat are at branch similarly R expected for B x = B = B, and the high J components of the R branch (It can be mentioned that this effect tend, therefore, to bunch up. important so that the components of the R sufficiently can become
farther
down
branch start moving back to lower frequencies for very high J values. The band is then said to have a band head. Such behavior is observed
only in electronicvibrationrotation bands.)
lead to values of
Analysis of the rotationvibration band can, as Fig. 74 suggests, It should be clear from Fig. 74 that the fii and B
.
component
of the
R
J
of the
gives information
on the rotational spacing in the upper vibrational level. Similarly, the difference in the frequency of the component of the R branch and that of the P branch that end at the same value of / in the v = 1 level gives
HO
information on the rotational spacing in the lower vibrational level. From the rotational spacings in the v = and v = 1 levels, one can
deduce values of B and B u Furthermore, values of B and S t can be obtained, from various pairs of transitions as a function of J, and any
effect of centrifugal distortion
can be recognized.
to values of
5 and B\ can be deduced by taking the appropriate differthe P and R branch components.
the rotational structure of a vibration
An
1
the v
and v
states can
be deduced from
in
The difference
dashed
spacing
in
the v
J 4
=1
1
*
t I
!
4
i i
I
!
I
i 1 1
1
1
'
i I
i
i
i
1 ! 1
i
I
I
1
i
i
ROTATIONVIBRATION SPECTRA
Ml
P and R components that start from the same J value, one has (10) 9b(J) ~ 9p(J) = 25 (2J + 1) starting from the component An evaluated. R be which B can from on level end the same the J 2 starting from P component + J level and a
Thus
for
X x
level in the
upper
state.
obtain,
by writing J
in the
components and J
+2
v P (J
+ 2) =
of B,
25
(2J
3)
(11)
From
can be obtained.
of I
The dependence
and therefore
and
r,
on the vibrational
Some
Also shown in the table are values for B. and r, which are deduced, by means of the formula B v = 5, a e (v + i) and the measured values of , for at least two vibrational levels. These results correspond to the equilibrium bond length, i.e., the bond length
are given in Table 71.
corresponding to the
minimum
One
This
r t is significantly different
from
makes
in
itself
mentioned Chap. 5, polyatomic molecules from which additional bond lengths or angles can be determined. The assumption of constant bond length with
would appear to be valid to a very good approximaFor the v = state, which is tion for the equilibrium bond length. spectral studies, a substitution usually what is studied in pure rotational
isotopic substitution
of, for
example,
for
lowers the v
way from
the value r
State of a Molecule
B.
r.
o,(
j)]
Molecule
5. (cm')
a,
(cm 1 )
(A)
ro(A)
0.7505 0.7495 0.7481 1.2838 1.282 1.1307 1.097
n(A)
0.7702 0.7668 0.7616 1.3028 1.295 1 1359 1.102
.
H D
HD
2
HC1 DC1
CO
'
for the Hcontaining
bands can can be obtained for different and these can be safely assumed to remain constant with
re
compound
to r e
If rotationvibration
isotopic substitution.
Exercise 72.
4.8
of
3.
14
10 24
g,
force constant of
first five
10 6 dynes/cm.
(a)
Draw
to scale
(b) Draw vertical arrows to represent the transitions that would occur in an absorption study of the fundamental band. (Place the arrows so that the one corresponding to the lowest energy change is at the left
and the highest one is at the right, as is done in Fig. 72.) (c) Pick out two transitions, and therefore absorption lines, that could be used to calculate B and two that could be used to calculate Si.
LINEAR MOLECULES
Two
molecules.
the vibration
is
is parallel
which
will
If
moment
is
perpendicular
to the molecular axis, a different set of selection rules apply and the rotationvibration
74.
band
is
Parallel
When
dipole
moment
is
concerned,
in
no way
different
and resulting band shapes are from the simpler linear molecules,
selection rules are Av
Thus the
= +1 and
i.e.,
AJ = + 1, and the
cules.
rotationvibration
The treatment
of the previous
bands of linear molecules and leads, for the fundamental vibrational transition, to values of S x and S a (Values of Si and 5 would be expected to depend somewhat on the particular vibration being studied; the value deduced for B e should be
section can also be applied to the
.
6
c a
_o ee
o c
o
q z
o c
o
<
8
UOISSIIUSU&ll
S
IU J9J
d
143
T f h
'44
all vibrations of the molecule.) The problem of deducing bond lengths from the single experimental result, B or /, is, of course, the same as that encountered in studies of pure rotational spectra.
It is of interest to point
no permanent dipole moment. It is only necessary for the vibration to be such that there is an oscillating dipole moment. The antisymmetric stretching vibration of C0 2 0=C=0, and that of acetylene, H H, are examples of vibrations which lead to rotationvibration absorption
,
C^C
bands.
From
The statistics followed by the like atoms of molecules such as CO 2 and C2H2 lead, as discussed in Sec. 55, to the decrease in statistical weight of some of the rotational levels or to the absence of some of these
44.
2
J..
,
(antisymmetric
stretching
vibration)
^Nmhpf
7
5
J I
It'
I
"I"
!._,,
444U
FIG.
76a
The
energylevel
dia
gram and
like
transitions of
a molecule
C0 2
ROTATIONVIBRATION SPECTRA
levels.
145
The appropriate
COJ 6 an example
,
in
which the like atoms have zero spin and obey BoseEinstein statistics, The absorption band that results from the is shown in Fig. 76a.
asymmetric stretching vibration is also shown in Fig. 766. Although the appearance of the band does not immediately indicate the effect of the missing rotational levels, one finds that the spacing of the components is twice 2B and that the central gap is half again as large as the spacing in the P and R branches. The molecule acetylene illustrates the case where Fermi statistics apply since the hydrogen nuclei have spin %. (The carbon nuclei have no spin and, therefore, do not have an effect.) The alternation in
statistical
is like
that of
2,
and
this
FIG. 76b
parallel
band of
CO2
and
like
E M
C
146
5
A3
2
1
j1
__
t
"
lift
4
3 2
l
1
j
FIG. 77a
1 i
of a molecule like
Cs=C
H.
components shown
in Figs. 77 a
and
b.
Bending vibrations
of
linear
molecules
have
oscillating
dipole
moments that
are
At;
= +1 P
and
AJ =
0,
+1
(12)
R
Q
branch corresponding to the AJ = transitions. The appearance of such bands is illustrated by the absorption band corresponding to the bending vibration of N 2 shown in Fig. 78. The
bands, a central
principal
new
feature, the
AJ =
transitions.
upper vibrational
same
/ * J
transitions
I E
E
i
o
.c
6 i X
1 o 5
E
<
uoissiujsuej)
)u J9d
148
would
Po
The
fact that
Si
is
smaller than
leads to
somewhat Q com
values.
The Q branch
asymmetry.
in Sec. 64,
vibrations of a linear molecule are, as mentioned doubly degenerate, and the two perpendicular motions of the molecule can be coupled to show that in this vibrational state the molecule has angular momentum as a result of this vibrational motion. This
The perpendicular
angular
momentum
is
about the figure axis leads to some additional feaThe lowest J value for the v = 1 state,
1
J =
momentum
that
N 20.
NjO
in
a vibrational^ excited
2,840
2,820
2,800

P(cm"
2,780
1
2,760
)
2,740
2,720
U?
momentum
value
rotation
is split
The angular momentum, furthermore, couples with the overall of the molecule in such a way that each J level of the v 1 state
levels that result
can be attributed to rotation of the These finer details can, however, best
They will occur again in our study of the rotationvibration spectra of symmetrictop molecules and will be discussed at greater length there.
be passed over here.
SYMMETRICTOP MOLECULES
The infrared active normal vibrations of molecules like 3 C1 and benzene, which are symmetric tops because of the symmetric arrangement of the atoms, have their oscillating dipole moment either parallel to the
unique axis of the molecule or perpendicular to this axis. As for linear molecules, these two types of vibrations have different rotationvibration selection rules and therefore different rotationvibration
76.
CH
band shapes.
Parallel
Vibrations that lead to parallel bands can be illustrated by the displacements indicated in Fig. 79a. All these vibrations have an
oscillating dipole
molecule.
moment along the unique axis, the figure axis of the For such vibrations the selection rules for the rotational
AK =
and
AJ =
0,
if
K *0
(13)
AK =
(14) in
AJ = 1
if
These rules can be combined with the energylevel expression, Eq. Chap. 5, for the rotational energies of a symmetrictop molecule
ijK
= S J(J
+
are
l)
(I
_ S)K>
J =
0, 1, 2,
(14)
.
.
K=
where
0,
1, 2,
/ and
quantum numbers,
and
A is the rotational constant is the rotational constant for the axes perpenThe
transitions that constitute the parallel
band can then be represented on the energy diagram of Fig. 710. If the dependence of the moments of inertia on the value of K is small, the spacing within each set of levels with a given value of K will be almost
150
V
,//
J
FIG. 79
and
(b)
ROTATIONVIBRATION SPECTRA
151
i.e.,
and J(J
1)B
to the total
given value of
Figs.
band from the transitions within each set of levels with a K can be shown as in Fig. 711. One should notice, as both 710 and 711 show, that for the higher K values the low values
not occur. This follows from the requirement that, since determines a component of the angular momentum while / determines
of
FIG. 710
J do
transitions that
are
J
11
10
87
6
54. 3. 2. 4=
10"
K4
K=3
K=2 K=l
K=
152
11
J_L
.11
L
I 1
I
lliii
I I
I i
K=i
l
I K =
,
Ml
i 1 1 1
K=2
K=3
L
Jh.
iii
J
I I
=4
'
K
=5
^nULUlh.iLilUUu^
FIG. 71
1
The components of a parallel band showing the contributions from each of the
levels of the v
state.
to or greater than contribution shown feature each this Outside of for any allowed state. = for the (except branches P, and R in Fig. 711 consists of simple Q,
contribution which shows no Q branch). The appearance expected for the total band is seen to be borne out by the absorption band of CH 3 Br
shown
If
in Fig. 712.
and
or at least
an aver
age value of B, in the same way as previously indicated for diatomic With such data the moment of inertia perpendicular to the molecules.
figure axis is obtained.
77.
moments perpendicular
to
accompanying the
vibrational transition
is
AK = 1
The
&J =
0,
(15)
undercan occur in a perpendicular band. The complete band can be of consist subbands stood in terms of a summation of subbands. These
ROTATIONVIBRATION SPECTRA
153
S
FIG. 712
3
lim Jd
8
The P
uoisnuKueji
branch
is
A parallel absorption band of the symmetrytop molecule CHsBr. partly resolved, while only the contour of the ft branch is obtained.
154
all
K. and type subR 1, the P, Q, Thus, as shown in Fig. 714, for K bands result from the AJ = 0, 1 transitions. Similar subbands occur For each initial K value, except K = 0, for K = 1 > 0, and so forth.
the
0,
AJ =
+1
*
one gets two subbands corresponding to the sets of transitions that occur within AK = +1 and AK = 1. The total band, as the experimental
FIG. 713
The energy
levels of
transitions that
are
K=
+
II
+
II
+
II
+
II
II
II
II
o
I.
a
o
o
a.
8 S .C M

o
II
e
II
II II
*7 h^
>
A)
O _ u
c
*
155
156
The spacing
level expression
of these
h. K
= BJ(J
1)
(A
 B)K*
that result in the
of v
(16)
and the changes AK = + 1, AJ = and B are taken as independent band origin by to, one has
For
branches.
If
and
if
AK = +1
P 0ta .nch
= =
&+(A
+ l)  K*\ w+(AB)+2(AB)K
B)[(K
2
iorK =
0,1,2,
(17)
ForAK= 1
Sflu.
= + = +
S,
(A (A
1, 2, 3,
(18)
The spacing
methyl
halides,
of the
branches of a perpendicular band can, accord B). For molecules like the
larger
where
is
arated and, as Fig. 715 shows, easily resolved. The alternation in intensity of the Q branches of the
CH
C1 band
with different
values.
The
1 is
which there are three rather than two identical nuclei not be given here. (See ref. 1, page 406.)
Exercise 73.
however,
B = C=
(a)
0.31
CH
Br are
A =
5.08
cm1 and
like
and v =
1 states,
to v = 1 energy difference.") but reduce the v = (b) On one diagram, indicate the transitions that occur in a vibration in which the dipolemoment oscillation is along the figure axis.
the other diagram, indicate the transitions that lead to the branches in a perpendicular type band.
(c)
On
UOISSIIUSUeJI U9D 1J
157
158
given molecule, one might find the rather disturbing fact that the
nowhere near the same in the different bands. The treatment given here, which leads to the expectation of a constant spacing of 2(A B), is, for some molecules, in error because of neglect of a coupling that occurs between the doubly degenerate vibrations, which can be combined to show an angular momentum, that lead to perpendicular bands and the rotation of the molecule. The coupling occurs through Coriolis forces, and the basis and effect of such forces
branch spacing
is
are discussed in
ref. 1.
The
can be calculated,
Obtain the infrared spectrum of a gaseous methyl halide. Determine A B for as many of the perpendicular bands as possible, and see that the values obtained are not identical. Compare with the value of A B calculated from values of the bond lengths and bond
Exercise 74.
angles reported in the literature.
PRINCIPAL REFERENCES
1.
Raman
Spectra," chap.
4,
D. Van Nostrand
Company,
The previous two chapters have suggested the importance of; molecular symmetry for spectroscopy. It has been shown that for nondegenerate
vibrations each normal coordinate, or vibration, of the molecule
either
must be
symmetric or antisymmetric with respect to any symmetric element. Furthermore, the previous chapter has shown that, for a symmetrictop molecule, the appearance of a rotationvibration absorption
determined by the symmetry nature of the vibration. In moreover, we will see that the wave functions that describe the behavior of the electrons of a molecule must conform to the symmetry
is
band
Chap.
11,
of the molecule
of a molecule provide
states.
and that the symmetry properties of the electronic states an important and helpful characterization of the
A
now be
symmetry
undertaken.
To avoid a
methods and results will continually be made to the study symmetric molecules. It should be emphasized, in this connection, that deductions based on the methods presented here are applicable to many areas of molecular spectroscopy and molecularstructure studies. Vibrational modes merely provide, in view of our
of general
of the vibrations of
tion of
symmetry arguments. This study can be divided into two major parts. First, the ways in which symmetry elements of a molecule are described and the ways in which the symmetry nature of molecular motions is determined and
t
159
160
Second,
it is
Point
Groups
0, are "sym
CO2 and
metric."
To proceed with a
it is
such symmetry,
cule
in
The symmetry
of
a mole i
its
equilibrium configuration.
All
symmetry elements
symbols used to denote them, in Table 81. These symmetry elements Each symmetry are best explained in terms of symmetry operations. element has a symmetry operation associated with it, and Table 81
(The distinction between symmetry, and symmetry operations, such as a reflection through a plane of symmetry, is necessary for an orderly treatment of the consequences of symmetry.) Various moleincludes a brief statement of these operations.
as a plane of
cules
drawn
so as to exhibit
and
82.
Illustration of the
symmetry elements are shown in Figs. 81 symmetry element E, which all molecules Its inclusion as an element of symmetry is
TABLE
81
E
a
i
No change
Reflection through the plane Inversion through the center
metry
C,
Axis of symmetry
Rotationreflection
axis of
symmetry
Rotation about the axis by 360/p deg Rotation about the axis by 360/p deg followed by reflection through the plane
141
become apparent later. The onlycomment that need be made about the symmetry elements is that, in diagrams such as those of Fig. 81, it is customary to set up the principal axis of symmetry vertically and, if a coordinate system is
dictated by considerations that will
further
used, to have the z axis in this vertical direction.
In a case such as
is is
a sixfold axis
and
It is
sym
metry elements.
If
investigated,
it will
be found that
only a few different combinations of symmetry elements occur. Each combination of symmetry elements that can occur is known as a point group, (The term point group is used because, as we will see, the symmetry operations that are associated with the symmetry elements of the molecule leave a point of the molecule fixed in space.
to a space group, as
is
This
is
in contrast
found in a
crystal,
to a
new
RG.
81
Some
in
cbc,
162
A summary
that can occur,
symmetry elements
i.e.,
symbols used for the point group are based, for the most part, on the principal symmetry element of the group and that the subscripts added
to
some
It is
of the pointgroup
symools further
tie in
TABLE 82 Some of the Point Groups That Are Important in Molecular Problems (The number of times a symmetry element occurs is indicated by a number before the symbol for that symmetry element)
Point group
Symmetry elements
Examples
c,
cs
C,
E E
CH,CHClBr
t
Cs
H 0,
2
E,i
CH,CHC1CHC1CH,
(trans.)
c
Cg Cj
E,a
E, Ct, 2a, E, Cs, Za, Ei C, <r E, C%, <r, t E, 3C 2 (mutually perp.), S t (coincident with one of the C 8 ), 2a & (through the S, axis) E, Ct, 3Cj (perp. to the C, axis), St (coincident with the Cs axis),
i,
NOQ
H,0, CHjClj
NH
HCC1,
CsSW
Cj
T>u
D,j
(cyclohexane)
Za*
3<r
D*=V
(mu
Xl2C == CH2
D sk
Da
D,
E, E,
C 3 3C 2
,
BC1,
3ff,
a\
t,
D.*
(perp. to the C axis), Ct and St (both coincident with C 4 ), i E, C t 6C, (perp. to the C axis), 6ff an, C t and C, and So (all coincident with the C axis), t E> C, > C s (perp. to the C axis),
4*r an,
,
C 4CS
C H,
4
(cyclobutane)
CH 6
(benzene)
H,, CO,,
HC=CH
<*>a ah, i
T* O*
E, 3Cj (mutually perp.), 4C, 6a, 3S 4 (coincident with the C 2 axes), E, 3C 4 (mutually perp.), 4C,, 3S 4
axes),
CH
[PtCl,]
6C 2
9ir,
4S, (coincident
with the
C), %
163
C2
\C
FIG. 82
drawn
in
ways
that will
elements for
all
It
is,
and
C dv
and
CH
3 C1,
illustrations.
which belong to these point groups, will be used in later These molecules, and the symmetry elements they conIt
C3
axis of
a two is a other revolution, and the third of a by a clockwise or a of revolution, twothirds a counterclockwise rotation by one of onethird of a revolution. The operation symbol C% designates the first of these and C\ the second.
symmetry
implies
different
symmetry
operations.
One
is
counterclockwise rotation
82.
of a molecule are
equilibrium configuration.
atoms
a molecule, such as occur in a translation or rotation of the molecule, or a vibration of the atoms of the molecule, can be related to these symmetry elements by means of the symmetry operation associof
symmetry operation to a molecular motion is best by means of arrows along the cartesian coordinates associated with each Atom of the molecule. One of the rotations and one of the translations, of the H 2 molecule are so described
Application of a
first
done by
164
Translation in the
direction
(T
FIG. 83
H2O
molecule by
means of displacement
in Fig. 83.
tration
CH 3 C1 is also used as an illusand the three translational motions are represented by vectors
first
Let us
molecule, which
an example of a molecule
The symmetry
operations corresponding
When
this is
illustrated
motions
Ty and Ry
for
of
or
similar manner, a
+1
or
symmetry operation acting on the displacement vectors that correspond and rotations of the H 2 molecule. (As the
FIG. 84
vectors.
Fig.
82
is
used.)
CI
y
s
^7
.'S
T,
165
The
represent
molecular vibrations.)
The results of such diagrammatic analyses can be put in a form that more convenient for mathematical extension by writing the operation of a symmetry operation on a molecular displacement as, for example, for
is
C*(Tt )
to the
and
C 2 (ffv )
These symbols are to be interpreted as "the operation corresponding C 2 symmetry element acting on the molecular displacements Ty
and
tion,
R v ."
The
result, that the vectors
c.(rr )
(i)(T)
(i)
and
C,(fl,)
= (D(B,)
one recognizes the reason for the use of
(2)
With
this procedure
+1
and
to represent symmetric
When
degenerate
will
+1
and
trans
known
Draw
molecule in the x and z directions and show that to the symmetry elements of the molecule result in either no change or a simple reversal of these vectors. Do the same for rotations about axes in the x and z directions and for the
to translation of the
When
it is
H2O
molecule.
.Or**
^H
^H
n^
166
energy levels because the moments of inertia about the axes in these two directions must be identical. Similarly, certain vibrations of such molecules will necessarily have, as a result of the molecular
tical energylevel patterns.
symmetry, iden
It follows, as
we
considered, they cannot be treated separately. This behavior can be illustrated by considering the effect of the symmetry operations of the CH 3 C1 molecule on the degenerate set T x and T v
.
atom
in the translation
Tx and
is
shown
(Similar
H atoms.
These
will
behave in an identical
manner to the vectors located on the axial atoms, and since the effect of operations on them is a little harder to imagine and draw, they are not included.) Let us now consider the operations C 3 (T X ) and C 3 (T y ). The
FIG. 86
molecule CH3CI.
The effect of the symmetry operations on the translations Tx and Ty of the Cj, The diagrams here correspond to end views, from the top, of Fig. 82.
H~TX
<r,
Operation
C%
7"= 1 x
X?T
Operation
C\
Operation *
n+"^?i!rv
r x + Y, x =T
t,=>+t{Etx  T
2
*
rx =ir,+or
r,= OT.XTt
*~TX
Operation oj
x =>Tx
+~&Tt
= jT, Y T r x +T u =^T
167
C3
when
the operation
Tx and Ty
Now, and
Tx
unchanged or reversed
of
in direction.
As
T x and Ty by
W,)
as
= 
i (T.)
^
I
(r.)
(3)
Ty vector by
C(Ty )
+ ? (T x)
(T y)
(4)
One
sees that
T x and Tv
It is therefore con
symmetry element C3 on
Tx and Ty by
*()(;!
In a similar
if)
describe the effect of the
transformation matrices.
all
Thus one
C3,,
group
of matrix
in this chapter.
(5).
168
C3
_ V3\
2
1
will play an important role in later enough to recognize that they allow the effect of the symmetry operation to be represented in mathematical rather than diagrammatic forms.
work.
is
83.
A brief introduction can now be given to the ways in which the behavior of molecular motions with respect to symmetry operations is
usually tabulated.
Some
is
material
is
studied.
arise when the motions of a molecule belonging to a given point group are investigated can be arranged in tabular form. The behavior of the motions of 2 0, or in
fact
any
symmetry
operations,
is
given in
Table
for
83.
Tz
This table summarizes the fact that the transformation matrices are +1 for each symmetry element; for R they are +1 for the
,
symmetry elements E and C 2 but 1 for a, and a' and so forth. v Since, as we will see later, a number of different molecular motions,
;
TABLE 83 Summary of the Transformation Matrices for the Symmetry Operations for the Translations and Rotations of the
C 2
Molecule
H2
<r
Csu
E
1 1 1 1
C,
1 1
T.
1
1
1 1
1 1
1
R,
Rv)
Tx
T
1
Rx
169
various electron orbitals for the molecule, transform with the transformation matrices given in one
row
symbols for each row. The procedure is to designate a row by A if the transformations are symmetric with respect to the principal axis of symmetry and B if antisymmetric with respect to this axis. Thus the first two rows of Table 83 would be labeled A and the second two B. In
order to distinguish the two
first
written, as
Ai and the
Similarly, the
two
and
2.
Thus, with this added notation, the sets of transformation C 2r symmetry are given in Table 84.
The rows of such a table are said to be symmetry species to which motions of a molecule or electron orbitals of a molecule belonging to the point group of the table can be assigned. A slightly different notation is used if the molecule contains a center
Then one uses, instead of the subscripts 1 and 2, a subsymmetry species that is symmetric with respect to inversion at the center of symmetry and u if it is antisymmetric with respect to this
of
symmetry.
script g for a
operation.
The transformation matrices that are found for the C 3, point group, Tz and T in the previous section, leads to degenerate sets of translations and rotations, are summarized in Table 85. It turns out, as we will see later, to be sufficient for most purposes
a group which, as illustrated for
to tabulate, not the complete transformation matrices, but merely the
sums
This
procedure leads, as can be readily checked from the matrices of Table 85,
to the
summary
86.
of the
symmetry behavior
for
3.
molecules shown in
doubly degenerate symmetry species is generally labeled Table E, not to be confused with the identity symmetry element, and a as
TABLE 84 The Transformation Matrices for Cj, Molecule with Symbols for the Different Behaviors with Regard to
Symmetry Operations
c,
E
1
1 1
Ct
1 1
a.
Ax A,
Bx B,
,1
1
1
1 1
1 1
1
T. R.
Ry, T* Rx, Ty
1
' '
73
^*
'
*
.
s
03
6i s as
6,"
a*
&,
8a
a
h
1
+
IN
ICC
1
^b"
>
>r
i
w
Q.
<*i
win
~~ +
~b
1
h
IN ICO
o
e
>r
+
"5
,^^ o h
j
iH
i
1
o
+
N 
r\
'
t*
in
i
1
o*
i
>r
+
*>l <\
l IIN
1
+
'",
rt
N
1
i
ICO
>r
i
^^ o
Kl
.1
rH H
+
V
00
a CO <
170
171
Matrices of a Cj Molecule
Cj,
E
1
c,
CI
1
1
<r
1 1
A,
1
1
1
R,
(R,Ry), (T,Ty)
1
X
or T.
and 85
is,
sum
transformation matrix.
the matrix
of
+1
or 1,
itself.)
The
and
Table 85
are typical.
only one column for each type of symmetry element. symmetry elements in the class is then indicated at the top of the column. Thus for the C 3, point group one abbreviates Table 86 and writes the
information as in Table 87.
The
and
basis, properties,
and uses
Their
is
introduction here
used.
One will notice in many advanced texts on spectroscopy and quantum mechanics that such tables are given for all possible point groups. (See, for example, G. Herzberg, "Infrared and Raman Spectra," D. Van Nostrand Company, Inc., Princeton, N.J., 1945; E. B. Wilson,
J.
McGrawHill
Book Company, Inc., New York, 1955; and H. Eyring, J. Walter, and G. K. Kimball, "Quantum Chemistry," Wiley & Sons, Inc., New York,
TABLE 87
The Sums of the Diagonal Elements of the in Con
densed Form
Cg
E
1
2C,
1
3ff
A,
At E
1
T. R,
(Rx,Rv)t (Tx,T v )
1
172
The first of these references also gives a detailed discussion, with examples, of symmetry elements and point groups.) It can also be mentioned here that, since the sum of the diagonals of a transformation matrix is known as the character of the transformation
1948.
many
symmetry behavior are known as the symmetry point groups. The character table for any point group can be deduced by finding
the transformation matrices for various motions of a molecule belonging to that point group. Little difficulty will be encountered in checking
some of the smaller, nondegenerate character tables by this method. A number of general properties of character tables will, however, be developed later, and it will then be easier to understand the larger character
tables containing degenerate types.
The introductory summary of molecular symmetry has now been Before making use of the quantities introduced here, an extensive digression into some of the general mathematical properties of the transformation matrices and character tables will be made. We will then see how the character table can be used to deduce some results
completed.
that are of great importance in molecular spectroscopy.
GROUP THEORY
An apparently rather abstract mathematical subject called group theory turns out to be directly applicable to investigations of a number
symmetric molecules. The theory can, for example, symmetry operations that have been treated in the preceding section and can be used to draw a number of important deductions regarding the nature of the vibrations of symmetric molecules and the electronic properties and electronic transitions of such molecules. Some of the mathematical features that can be ascribed to general, or
deal with the
abstract, groups will be pointed out, and deductions of properties of such groups, which are important for molecular spectroscopy, will be made. The previous treatment of symmetry elements and symmetry
of properties of
some
given a
To be
173
can be objects, quantities, operations, and so forth, must conform to four requirements. It should, perhaps, be pointed out immediately that these requirements may appear "unreal." That they make the
term group a useful mathematical concept will be apparent as our study of the theory that can be built up for groups develops. is said to form a group if the A set of elements P, Q, R, S,
. . .
a rule for combining any two elements of the group; and the combination of any two elements according to this rule leads to the formation of one of the elements of the group. Commonly one calls
1.
There
is
we
will see,
the
procedure need not be the familiar multiplication. When the elements P and Q are combined one writes PQ. The first requirement for a group
is
that there be a rule which makes the combination PQ meaningful and, moreover, makes PQ equal to an element of the group.
2.
must hold for the combination of elements. means that Thus if P(QR) Q and R are multiplied, i.e., combined accordand then P multiplies the element formed rule, ing to the appropriate requires law from QR, the associative
The
associative law
P(QR) = (PQ)R
The righthand
side implies that
is
(6)
(It should here be mentioned that the commutative law will not be stipulated as a requirement for a group. Thus PQ will not necessarily be equal to QP. One must, therefore, be careful to preserve the order
in
which elements are written.) 3. The set must contain an identity element, which we will designate by E. An identity element E is an element with the properties such
that
EP = PE = P EQ = QE = Q ER = RE = R
and
does
so forth, for all elements of the group.
(7)
commute with
4.
all
is
also
For every element of the group there must exist an inverse which an element of the group. An inverse is defined so that if S, for
is
example,
the inverse of
Q
(8)
QS = SQ = E
174
The
will
which
The
rules that
must be obeyed by a
set of elements
if
they are to
now be
illustrated
symmetry,
i.e.,
group.
The H 2 molecule was seen to have the symmetry C 2 , and the symmetry operations for such a molecule are those corresponding to the symmetry elements E, C 2 <f v and c' These operations will be recogt
, ,
.
if
is
successive operation
on the molecule by the symmetry operations. (One generally agrees if, for example, the combination CV, is written to operate first with the element on the right, i.e., <r,, and then with the element on the left, i.e.,
now see if the symmetry operations conform to the requirea group. 1. One can verify, by operating on various rotational and translational motions of H 2 0, that successive operations are always equivalent to the single operation of one of E, C 2 <r or <r' Thus t
C2.)
Let us
of
ments
EC* = C 2
<r,<ri
= C
= CW =
C*r,
2.
<t' v
(9)
etc.
is
a,
The
associative law
tested
by
as
<ri(<V,)?(r:C,)*.
We
find
Left side
<r'
(C*r v )
(<t' v
Right side
2 )* v
= E = (*> = E
<r'(ri)
(10 >
In a similar manner it can be verified that various ways of associating the elements in a sequence of operations lead to the same element; i.e.,
The
no change
It is
is
imposed on the
so that
symmetry operations
apparent that
EC = dE = C 2
*
etc.
(11)
175
To
that there
of the
C 2,
point group
we
see that
C2C2
= E
(12)
w, = E
oW.
= E
tb^is will
Thus, and
is its
not generally be
so,
C 2v
group
own
inverse,
Exercise 82. Verify by drawing the appropriate displacement diagrams that two successive symmetry operations on a translation or rotation of molecule are equivalent to a single symmetry operation of the the 2 molecule and that this single symmetry operation is a member of the
C iv
point group.
have shown, therefore, that the set of symmetry operations conforms to the requirements for a group, i.e., they are a group. In a similar manner, the symmetry operations associated with other point groups can be tested. It will be found that these sets of symmetry
operations similarly obey the group requirements.
We
Exercise 83.
postulates.
Using T, as a basis on which to apply the group operations, C 3 group do, in fact, obey the group
Exercise 84.
C 3v
Using T x and T y as a basis, verify that the elements of the group obey the group postulates.
Any
of a
group
is,
It is this therefore, binding on the symmetry operations of a molecule. involving molecular problems theory to group that ties abstract result
symmetry.
86.
Representations of a Group
Of particular importance
to be put
is
is
by numbers, or more genand these can then be combined by ordinary multiplicaor faithful, the multiplication of the
PQ
R,
number which represents the element R. matrices, which can be assigned to the elements
set of
numbers, or
of a
17*
said
C 2 point group can be used Customarily, representations are designated by T and the components of a particular V are written under the group
Again the symmetry operations of the
An
constructed by assigning
C 2t +1 to
apparently trivial but, in fact, imporgroup of symmetry operations can be each element. Thus one would write
E
(1) (1) (1) (1)
(The parentheses are placed about each number because, as we will see, they are onebyone matrices.) Since any combination of symmetry operations leads to one of the symmetry operations of the group, this is
properly represented by the multiplication
(1)(1)
(1)
(13)
Three other onebyone representations (the way in which they were deduced will be shown shortly) can also be written and a table of representations can be constructed. Thus the representations Ti, r 2 r 3 and r 4 can be given as
,
,
E
Ti Vt r,
(1)
(1)
c2
(1)
(1)
a.
(1)
(1)
(D
(1)
(1) (1)
(1)
(D (D
(1)
r4
(D
(D
It
all
properly represent
symmetry operations
of the point
group
C2
,.
To do
this
and investigates the ways in which the various representations rpu Thus
of the
For the Ti representation: For the r 2 representation For the r s representation: For the Ti representation
(D(l)
(1)
177
The result of the four multiplications is seen, in each case, to give the number which that representation attaches to a',. A similar test of other combinations will show that multiplication of the symmetry operations
is
Exercise 85. Test that the representations of the C 2 group faithfully represent the multiplication of several pairs of symmetry operations.
While these simple representations might have been discovered by trial and error, it is interesting to see that they are nothing more than
the transformation matrices discovered for
in Sec. 83.
We
must
now
see
why
group of symmetry operations. It is necessary to show, for example, that the transformation matrix for CV. is equal to the simple product of the transformation matrices To do this, one might investigate the operation equation for C 2 and <r.
of the
Cr v (Tx )
c' v (Tx )
(U)
The operation
C*r(Tx )
of
<r
on
Tx
will give
write
(15)
C,(+l)r.
acts only on Tx and cannot affect the pure number (+1). This implies that (+1) and C 2 can be written in either order, i.e., they commute, and one can write
The operation C 2
c.{T.)
In this
(+i)c,(r)
sees that,
is if
= (+i)(i)(2V> = (i)r. C2
is
(16)
<r
way one
represented
represented
by (+1),
(+1)(1) 
(D
Furthermore, since as Table 84 shows, the operation <r' v on T x changes Tx displacement vectors, one represents (r'v (Tx) by
1) Tx
if
C s and a,
(r'
are represented
by trans
CV, =
will
be properly represented
.
by the product
therefore,
It follows, of the transformation matrices of C 2 and <r v and this is an illustration of a general result, that the combination of symmetry operations corresponds to simple multiplication of the corresponding transformation matrices and that this combination is faithfully represented by transformation matrices. Although the transformation matrices dealt with so far do form
178
There
are, in fact,
an
infinite
number
of representations.
Some
of these that
These genmight
c2
GO'
(lit)
\0
1/
G
/l
?) 0\
G
/l
?)
0\
1
G
/l
1
0\
(O
\0
10}
1/
(o \0
o)
1/
o)
1/
\0
G!)
and so
forth.
(J
t)
?)
G 0
faithful representa
C 2v
Other large matrix representations can be found. A particularly important one for a given molecule is that based on the Sn cartesian displacement coordinates that can be associated with the atoms of the
Such a representation can be set up by writing the 3n carcolumn matrix and deducing, by looking at a diagram of the molecule and the 3n displacement vectors, the Zn X 3n transformation matrix for the particular operation. For example, in view of Fig. 87, the operation <r on H 2 can be seen to lead to the transmolecule.
tesian coordinates as a
FIG. 87
The
xh>.
effect of the
<r
coordinates of"
that x H
H 2 0.
One
sees, for
symmetry operation on the 3n cartesian displacement example, that xh transforms as shown into x< and
4
Operation
ZB'
SO. xii
"^H*
179
formation matrix
'
Xh
Vh
zh
'
xH
1
1
'
Vh
zh
Xh'
xH
Vh>
zh'
1
1 1
Vh'
Zh'
x
y
o
,
Xo
1
.0
1,
.
zo
group can similarly be found. In this way one would obtain a representation of the C 2 group consisting of four 3n X 3n matrices.
Exercise 86. Verify that the transformation matrices for a given molecular motion provide faithful representations of the symmetry operations of the C 3 , group. Do this for the onebyone matrices that are obtained when T z or R is considered and also for the twobytwo matrices that are obtained on the basis of (T X ,T V ) or (R X) R y ).
87.
In the preceding section it was shown that representations of small dimension, such as those involving onebyone matrices, could be built up to give any number of representations involving matrices of larger
Of much more importance is the process by which a largedimension matrix representation, such as the 3n X 3n one based on cartesian displacements, is broken down into representations which
dimension.
consist of matrices with as small a dimension as possible.
Representa
down
and those which involve matrices whose dimensions cannot be further decreased are said to be irreducible representations. We will find that for any given group, although there are an infinite number of reducible
few irreducible representations. Suppose that the set of largedimension matrices E, A, B, C, forms a representation of the group. New matrices can be obtained from these by what are called similarity transformations. Thus, if
.
.
there
is
a square matrix
/3,
with an inverse
/J
1
,
matrix multiplications
180
A'
B'
= = =
0r l A0 p~ Bp
l
(17)
etc. will
jS'CjS
now be shown
It is
B
=
did,
and
so forth.
this
D'.
To do
and D'
A'B'
D'
and obtain
p l
AWBp
/?
=
/3
p~ l D0
each other,
i.e.,
(19)
Now
since
and
8 :
= E =
1
;
(20)
and
since
EB =
ptABp = P'DP
Now we
on the right
can multiply both sides of this equation, on the by p~\ Since /3/3 1 = p~ l P = E, one has
by
/3
and
AB = D
Thus A'B' = D'
is
(22)
equivalent to
AB =
Now
all
it
might be possible to find a transformation matrix such that are of the form
.
.
(o 2)
(a,)
(23)
/(&i)
\
;
B'
(ft,)
\
where
. . .
(6 3 )
etc.
are square matrices of the same dimension, o 2 62, C2 oi, fti, c h If such transare square matrices of the same dimension, and so forth.
,
181
AB = D
equal,
ai&i 0262 03&3
or
A'B'
D'
if
'
= = =
di ds
<^3
(24)
It follows
that
a2 b 2
,
c 2,
and
so forth, also
form
or A', B',
C,
the repre
by
the" similarity
transformation.
If it is not possible to find a matrix /? that will further reduce all the matrices of a given representation, the representation is said to be
irreducible.
The transformation matrices deduced for the C 2 and C 3r point groups in Sec. 83 are irreducible representations. They are, as will be shown later, the only irreducible representations for these groups. Any
other matrix representation can be reduced to one or more of these
irreducible representations
88.
by a
We
of the
and
point
First it is necessary to define the order of a group as the number of elements in the group. The symbol g will be used to represent the order of a group. From the treatment of the C 2 and C 3, groups in Sec. 83, it should be apparent that their orders are 4 and 6, respectively.
As the heading
ible representations
behave
like the
components of orthogonal
vectors.
The orthogonality property requires that, if I\(iJ) is the matrix which represents the .ffth symmetry operation of the group in the j'th irreducible
representation,
ri(fl)iyfl) = X B
o
o
etc.
Vr
(/j)r,()
(25)
182
confirms this
r<(fl)r,(B) =
R
for
*j
C
2
(26)
group corresponds to
T^RMR) = I *
r X R
2
4
(27)
(R)T 2 (R)
etc.
Let us
now
see
if
3
irreducible representations
group where degeneracy occurs and one of the One can test the is a twobytwo matrix.
all
which we will now label as r 1; multiply, for example, the first row, first column elements of the third representation r 3 the sum of the products Likewise the sum of the squares of the elements of T is again zero.
,
6,
r 3 the
,
entries in the
column, for example, gives the value 3, the order of the group divided by 2, for any component. These results for the C 2 and C 3 groups are examples of an important
row,
first
If
Yi(R) mn designates
the
R symmetry operand r,(#)mv designates the m'n' component of the jth representation for the R symmetry operation, the general properties, which have
mnth component
of the
t'th
ation
been
illustrated,
can be expressed as
Ir
R
i (i2)
m rJ (i?) m
v=
i^j
(28)
I
R
r i ()r (R) mv
i
=0
m^
m',
iA n'
I URUURU = 
( 29 )
183
is
where g
is
t'th
irreduc
ible representation.
obeyed by irreducible
fact
they are
twobytwo or threebythree matrices, behave as orthogonal vectors By analogy with two and threedimensional
it is
space,
many
orthogonal vectors
only be g orthogonal vectors. C 2r group given in Table 84 form, therefore, a complete set for this fourthorder group. Likewise, for the sixthorder C3,, group, the two
the
onebyone and one twobytwo matrices, the latter contributing four "vectors," given in Table 85, form a complete set. One sees that we
now have
a
those that have already been reported for these point groups.
One has
way
of determining
all
tions of a group.
Verify that the elements of the transformation matrix C 2 group behave like orthogonal vectors. Do the same for the matrices of the representations of the C 3 group.
representations of the
89.
Exercise 87.
Characters of Representations
The characters of the matrices of a representation are defined as the sums of the diagonal terms of the matrices. It turns out that the
characters rather than the complete matrices can be used for many important deductions. This fact introduces a considerable simplification into the applications of group theory.
The character
is
of a representation of the
denoted by x(R)
The
as
x(R)
T R ) X m
(
(30)
is
not neces
is
the
?'th
Xi(R)
=X
r.(fi) mm
184
We
the
have already
if
constitutes a representation
new
group.
Now we
will
show
it
leaves,
and normal, the characters of the matrices unaltered. [The derivation, involving more matrix manipulation than previous work, need not be followed through. The student can proceed directly
similar
Q = pWe
then
(32)
xq
xp
$ lP$
is
(33)
written
t'th
diagonal element of
Q by
(34)
Qu =
X u
/3
G8" W*i(/8)
Now,
since
is
(T%
where
/3'
= 09% =
(35)
matrix.
written as
Qu =
I
kl
0)*G8)kP
of the diagonal elements of
(36)
Finally, the
sum
i,k,l
is
obtained as
X
i
Qu
=
=
J
kl
G9)*0) p
22 Kfl*G8)l p
i
2 &tiPw
=
ZP
S,
(37)
[The Kroeniker
Su
equals
1 for
= I and
for k
I,
(j8)(/S)k
185
We
xq
result
xp
(38)
This important result will be used when we investigate the irreducible representations that
We
see
that
if
the breaking
down
by
'(
)
(
(
sum
same as
and
groups will show that the characters, like the representation matrices
The
Xi(R)xAR)
for i
*j
(39)
and
X()().= R
The proof
from the
results
ff
(40)
We
have,
on irreducible representations,
?
where k
Ti(R) nm T,{R)w
for i
^j
(41)
TiiR^ViiR)^ = f
is
(42)
If
the
sums
now
components that are summed when the characters are formed. Similarly, the product of the characters of one representation by itself can be written out, in view of Eq. (29), in terms of the diagonal components
186
Ti(R) mm Ti(R) mm
= k
(43)
In this
way
is
obtained.
The expressions of Eqs. (39) and (40) give properties of the characters of two representations as one goes across a character table, i.e., one sums over the various operations of the group. It is interesting to notice also that one can relate the number of irreducible representations to the characters that appear in the column under the identity element of
the group.
This follows from the fact that the character of the repreis
The square
of this
number
number
of ''vectors," as
In view of
the discussion at the end of Sec. 88, one can write, therefore,
X \{E)
+
the
X \{E)
xKE) =
(44)
where
c is
number
all
In almost
be
possible to make use of the characters of the representations and the relations involving the characters that have been obtained here rather
and
Verify that the characters of the C 2 and C 3t groups, given 86, behave in the manner indicated by Eqs. (39) and
,
Exercise 89.
2t>
and
One
fies
symmetry
operations, simpli
grouptheory applications.
the
C3
and C\ are
operations
tions,
and
those for a v
<s'
and
<r"
The
C z and
Cjj
The
and the operations <r, a' v identity operation, having characters unlike that of
<r"
and
by
itself.
operations of the
C2
belongs to a class by
187
and Q,
l
In abstract group theory a class consists of a set of elements, say of the group which, when subjected to the operation
X~ PX
where
and
X~^QX
which
is
is
member
of the set,
or Q.
C 3 and
3l)
The
noted
E*C 3E = C 3 Cj 1 C 3 C 3 = C 3
(Cfl'CCJ
P7K7*r.
aE ^C\C
E~
i
= a 3 = C
=
CI
c\
(CIV'CICI
ff^CJir,
=
3
C\
= C\ (O'cv: = c\
(oi)>C*:
= C (O'CX = c 3 w:y*cy: = c 3
We see that, when C 3 and C\ are subject to a similarity type operation by all the elements of the group, the result is either C 3 or C\. Thus C 3 and C\ constitute a class. In a similar way one could verify that E by itself and a v a' and a" form classes.
,
When
symmetry
to deduce that the representations of all members a class have the same characters. The matrix of each member of a class transformed into another member of the class by at least one of the
transformation matrices.
the same character.
In
way
all
and C 3v character tables. The detailed working out of the combination X~ PX is not usually necessary in order to decide which symmetry operations belong to a class. Geometric consideration will usually be sufficient, and one will find that rotations such as C 3 and C\ and reflections through similar planes such
Cj,
X
as
<r, <r'
<t"
constitute classes.
When
is
all
symmetry
188
a square array.
if
That
this
must be number
so can be
fact that,
class,
allowance
is
of elements, say n, in
each
R now
and
Over
all
lVnkxi(R)][Vnixi(R)]
for i
*j
(45)
and
Over
all classes
[Vr*xt(R)]lVnixi(R)]
(46)
Thus the \/n^Xi(R) terms behave as components of orthogonal vectors, and there can be only as many such vectors as the dimensionality of the space allows. Thus we conclude that there can be only as many representations as there are classes.
recalled, to the previous
This conclusion
is parallel, it
should be
many
representa
It
should
mentioned that the factors n are usually placed at the top of the character table rather than as part of the characters themselves, but this does not alter the argument given here.
811. Analysis of
a Reducible Representation
The final aspect of abstract group theory that must be dealt with we can proceed to some applications is the question as to whether, given a reducible representation, there is any convenient way to deduce what irreducible representations make up the reducible one. In Sec. 87 it was pointed out that, in principle, one could find a similarity transbefore
irreducible representations appeared explicitly.
formation to convert the reducible representation to a form in which the In practice there is no
convenient
this.
way
is,
There
dis
covering
in'
a given reducible representation. Since any reducible representation can, in principle, be reduced it contains by a similarity trans
x(R)
 l
aiK(R)
189
where x(R)
is
c irreducible
number
of times the
We
over
first
sum
all
symmetry operations R.
In this
way we
obtain
x(R)xi(R) I R
(48)
Now the
?*<>*<> j,
tit]
can be used on the right side of Eq. (48) to convert Eq. (48) to
x(R)xi(R)
?
or
at
ckg
=
\
X
if
x{R)xi ( R)
(5o)
Thus,
from a
number
of times
summation over all symmetry more convenient to have the corresponding expression where the summation is over all classes of symmetry operations. For
expression requires the
operations.
It is
The above
this
one writes
1
V
Over
all classes
nnx(R)xi(R)
(51)
where n R
operation
is is
the R.
number
which a typical
We now have the basic results from abstract group theory and can proceed to apply them to problems in molecular spectroscopy and molecular structure.
The methods of application will be illustrated in the remainder of the chapter with problems based on molecular vibrations. Similar applications to electronic structure and electronic spectra will be made in
Chap. 11 when these subjects are studied.
190
Exercise 810.
The characters
group are
of.
4, 0,
irreducible
2, +2
and
Exercise 811.
Deduce the
7, 1,
and
812.
and
Molecular Motion
The
3re
effect of the
of a molecule
how
the
normal coordinates (including translations and rotations) are changed when the various symmetry operations are performed. These transformation matrices would constitute a reducible representation.
3ra
The
normal coordinates are said to form a basis for the representation Since each normal coordinate must transform according of the group. to an irreducible representation, or a degenerate set must transform
according to two, three,
representations that
particular interest.
etc.,
make up
It follows
that
it is
how many
times the various irreducible representations occur in the reducible representation to discover how many of the 3n normal coordinates belong
to the various
symmetry
species,
i.e.,
irreducible representations.
We
basis of the
initially
unknown
rotations).
states:
if
helpful result
two representations
only in their basis coordinates and if the coordinates of a group combinations of those of the other base, the two linear are of one base representations are said to be equivalent and the characters of the two
(The result is based on the fact that two such to be related by a similarity transformashown be can representations can resort to the much simpler procedure one this theorem With tion.) representation on the basis of the 3n reducible the of constructing Such transformation matrices were cartesian displacement coordinates.
representations are equal.
deduced for the H 2 molecule in Sec. 86. The character of this reprethe sentation, which is found rather easily, will be the same as that for coordinates. normal the 3n on representation based
191
To
is
on the diagonals
done,
To show how
2 0.
this
can easily be
we again
The 3n
cartesian coordinate
by equations
of the
Xh Vh
Zh
,
4
XH
Xh'
=
z',
Xfj
2/'o
Transformation matrix
Zh'
x
2/o
J
.
1.
Zo
can be found by inspection of diagrams such as that shown for the symmetry operation ct in Fig. 87. The four transformation matrices
for the
10000000 010000000 001000000 000 100000 000010000 000001000 000000100 000000010 000000001
0^1
192
1
0'
1
1
1
1 1
1
1
1
(T
1
1
1 1 1 1

1
1
.0
<
'
1
1 1 1 1
1
1
One should
first
metry operation leaves the position of an atom unchanged. One can deduce the character of the representation matrix, therefore, by concerning
oneself only with the cartesian displacement vectors of the
do. not
atoms that
change positions as a result of the symmetry operation. With this recognition and the fact that the vectors of unchanged atoms in
molecules like
effects lead to
are left
+1 and 1,
193
C2
av
9113
The sums
of the diagonal elements of the complete transformation
One might further notice that simple, general statements can be made about such characters. When an atom is unchanged in position
as a result of a
to the
C2 C 2 character.
operation,
Similarly,
it
if
it
if
will contribute
a net
contribution
any atom
is
unchanged
a
in position
by a
reflection
through a plane,
Furthermore,
will contribute
+1
to the appropriate
a character.
an atom
is
symmetry and by
will
be
made
to the
more
tributed
by atoms when,
as a result of a
C 3 d, and
,
in
such cases.
FIG. 88
i.e.,
axis, to the
cos 6 sin 9
sin 6
cosd
1
*<Rolatiol,0>
"* (Rotation
fay
(1
+ 2cos 0>
(
9 and
+ * COS v)
IM
With these
unshifted atoms
of order 3w.
generalizations
we can summarize
Table
88.
make
is
This
done
in
With these
and
recipes,
one can
readily write
down
making the
of the various
symmetry
operations.
of the
Exercise 812.
3n dimension representation
Number
of Normal
Modes
it
sentation for a molecule could easily be set up, and in Sec. 811
along with the fact that each normal mode, including translation and
rotation as well as vibration, transforms according to one of the irreducible representations,
allow the
number
of
different
symmetry
types,
i.e.,
to be determined.
The
The
The characters
previous section as
were given
in the
Ci
av
it.
911
Now
one calculates the number of normal modes that transform
first
according to the
representation,
i.e.,
Operation
E
a
i
3
1
C2
C3, C3 ci, c\
3 1
u
1
a. c\
19S
(51).
Thus
M
= =
> i[9
n RX (R)xi(R)
Over
all classes
+1+
1 1
3]
= = =
Similarly,
a2
a,
= i[9 = #9 + =
i[9
1 1
3] 3]
+

2
(52)
and
a4
3]
r
If
= 3Aj + A 2
2Bi
3B 2
r vlb There
of the
= 2Ai
B,
(54)
are, therefore,
two vibrations of the symmetry type A\ and one symmetry type B 2 One can verify that the displacements dis.
played for
symmetry
types.
In a similar
classify the
The importance
tionvibration
parallel
such classifications
is
CH X
3
because of the previous discussion of rotaof the different types of vibrations. of the vari
Exercise 813.
CH
3 C1.
It is
mode
of CO2,
i.e.,
*""
0=C=0
>,
have no
moment and
magnetic radiation.
moment
is
we
will
now
will
see, to
decide for
i.e.,
be active,
for
196
moment
will
not necessarily
As was pointed out in Sec. 45, a fundamental vibrational transition, from v = to v = 1, can occur with the absorption of electromagnetic
radiation in the vibrational energylevel pattern corresponding to the
if
fMQ<)n*MQi)
dr
dr dr
JMQi^vUQi)
or
SMQi)n*MQi)
is
nonzero.
an observable quantity,
indistinguishable orientations of
of the three transition
by Eq. (446). Since this band must have the same value for all the molecule. It follows that for any
it
moment
integrals to
the
value of the integral must be unchanged for all symmetry operations on the
molecule.
It is
now
symmetry operations
integrals.
The dipole components can be represented by the charge separations shown in Fig. 89. It should be clear that these dipole components will transform under the various symmetry operations in exactly the same
way
Tz Ty and T
,
It
and ry2
will
The
lAvib
vibrational
wave function
= v(Qi)v(QtMQ)
state,
<p((?36)
all
(55)
where
vibrational
quantum numbers
are zero,
FIG. 89
a molecule and
cartesian axes.
197
one has
<A (1>0)
<Po(Qi)<Po(Qz)<Po(Q3)
"
"
"
<Po(Qine)
(56)
For harmonic
oscillator
wave functions
this total
const
2wvk/h.
[eTii ! e" Q
.e~ro >'>]
(57)
where
<y k
Now
the effect of a
can be investigated.
in ^_o are
tions,
only the squares of Q's occur in the expression, the nondegenerate terms
a doubly degenerate
of
unchanged by the symmetry operation. Degenerate vibrapair, for example, have the same value of vt,
yk
.
and therefore
ertQ^evM 2
A
.
e yt(.Q t '+Qi'y
the value of Q\
Q]
unchanged.
lead to f_o,
operations.
It follows, therefore,
i.e.,
that
all
symmetry operations on
under
all
^_o
the
ground vibrational
state is invariant
symmetry
for a molecule in
excited to the v
1 state is of
=
=
(const) (Q 4 )(fc_)
v
wave function
is
of the
form
(const)' QieTe*
v,
1,
Similarly,
if
a degenerate pair of
1 level,
normal
coordinates.
effect of the
symmetry operation
R R Hy
yx
*
as
>
p.
YWO
*.,!
^ Tt.(R)p. R
tf'rO
^ T Qi (R)i Vi =i
result of the
The
198
J^rtii dr  ?T.(R)?Q<(R)N'vwJ'v i dr
i
(60)
The previous result that all symmetry operations must leave the integral unchanged if it has a nonzero value means that TtAR^qXR) must be unity for each and every symmetry operation. The normalization and orthogonality characteristics of representations show that only if Y Tx and T Qi are identical representations can the
and so forth.
product of T Tl (R) and T Qi (R) be unity for every R.
the transition
It follows that
moment
=
,
to v
if the
.
normal coordinate
coordinates
With
this result
and an analysis
of
belong td the various symmetry species, one can determine the number
fundamental transitions that can occur for a molecule symmetry. The argument can, it should be mentioned, sometimes be turned around so that the geometry, and therefore the symmetry, of a molecule is determined from the number of infrared absorption bands
of infrared active
of a given
will only
The requirement
of the
for a
Raman Raman
shift
type
J*o(Q<)**i(Q) dr
SMQi)<**MQi) dr
etc.
,
,
be nonzero.
etc.,
reason that
, ,
symmetry
species of
TX T X Tx Ty Raman
etc.
active
symmetry
species as one
TX T Z Tx Ty and
,
so forth.) of the
Exercise 814.
Which
CH
bands corresponding to fundamental transitions, and which be parallel and which perpendicular vibrations?
815.
Many
since
1W
than that of the other atoms of the
mass
is
usually so
much
less
It turns out that in such a case molecule, often lead to such vibrations. or at least visualized, in treated, can be molecule the vibrations of the
terms of separate vibrations of the molecular skeleton and vibrations of the hydrogen atoms of the molecule. This separation is of great aid in assigning the observed infrared absorption bands to normal vibrations
of a molecule.
CC1 3
CH CC1
2
will
to the
point group.
Let us
first
calculate the types of the vibrations of the molecule without the two hydrogen atoms. The characters of the reducible representation for
tljis
84, to
be
27
1
The number of vibrations of the different symmetry types atom fragment can now be calculated as
a!
of this
heavy
a2
a,
at
+ 1 + 5] =
1
8
* '
1
1 1
+

1 1
5]
5]
+ 5]
=5 =6 = 8
Removal
of the translations
r h
= 7 At
+ 4A + 4B + 6B
(62)
i.e.,
entire molecule,
r vib
= 9^! + 5A
+ 6B! + 7B
(63)
The
additional
therefore, vibrations of
the types
PH.,.
= 2Ax
+ A + 2Bi + B
2
(64)
contains.)
200
not be
made without
It is, however, helpful to recognize that each hydrogen atom introduces one vibration that is essentially a C stretching vibration and two vibrations that are essentially bending ones. With this approach the six diagrams of Fig. 810 can be drawn for the methylene vibrations. These vibrations can be expected to occur, more or less disturbed and altered, in any molecule that contains a
CH
nized,
group.
characteristic of a
it is
CH
group.
When
some
of the
CH
and
CH
groups.
FIG. 810
Vibrations of the
CH2 group classified according to symmetry. The form of and the frequencies of the fundamental absorption bands depend
the molecule containing the
CH 2
group.
f
4 j(CH stretching)
v
.4,(CH Z bending)
v
2,870cm 1
= l,460cm _1
Hi
.H
rU**
.Jj
,H
H^
7
,(CH
T
stretching)
I
fljtCHj nuking)
v
h
* 2 (CHj
1>
wagging)
2,950001'
800cm 1
1,330cm 1
201
3 Analyze the symmetries of the vibrations of a Classify the group, and draw diagrams to represent these vibrations. diagrams according to symmetry type and bending or stretching nature.
Exercise 815.
CH
PRINCIPAL REFERENCES
1.
Eyring, H.,
J.
& Sons,
2.
Inc.,
J.:
New
York, 1948.
of
Bellamy, L.
Sons, Inc.,
&
New
3.
New
York, 1959.
*?^.
'J''
'':
<#
"
'&i3>
=
t:"'!"'
...
TVi V
'l
CALCULATION OF
VIBRATIONAL FREQUENCIES AND NORMAL COORDINATES OF POLYATOMIC MOLECULES
It
will
has been shown in Chap. 6 that certain natural, or normal, vibrations occur in a manyparticle system and that these normal vibrations
are characterized
by
particle
same frequency.
transition in that
Furthermore, weaker bands, due to overtones and combinations of fundamentals, may be observed.
For a diatomic molecule only one vibration occurs, only one vibraand only one fundamental transition
observed spectroscopically.
2,
The frequency
Chap.
cule.
of the mole
It is
now
necessary to see
how
fundamental transitions of a polyatomic molecule are related to the force constants and atomic masses of the molecule. We will also be interested in determining how the molecule vibrates, i.e., what the form of the normal coordinate is, in each one of the normal vibrations. When all
this
its
infrared absorption
is
spectrum, which
202
may
said to be
analyzed or understood.
203
The treatment
of diatomic molecules in
f ma relation in calculations With this approach it is necessary to set up for polyatomic molecules. expressions for the kinetic energy T and the potential energy U of the After an initial discussion of how this can be done for a polymolecule. atomic molecule, the form of the equations that result from substitution
of Lagrange's equation rather than the of these functions in Lagrange's equation will be considered.
Following
Finally, will be worked through. oped by Wilson for performing such calculations
91.
be outlined.
The
of the
atoms
each other.
that measure the positions of the atoms relative to a set of axes that
motion.
Zj,
move with the molecule as it undergoes translational and If the jth atom is located, in terms of these axes, by
ately written
rotational
x,, yj,
and
the kinetic energy due to the vibrations of the molecule can be immedi
down
as
r = *
,(*,*+.
# + 3)
(i)
This expression
tional problems.
is
One should note that the orthogonality of the cartesian displacement coordinates results in an expression that contains squared terms and no cross products. It is important to remember that a motion described as a vibration must not involve a net translation or rotation of the molecule. This requirement is imposed by requiring that no movement of the center of gravity of the molecule and that no angular momentum be imparted to the molecule by the velocity components Xj, yj and In this way the
,.
kineticenergy expression of Eq. (1) can be used along with the relations
j=i
mjXj
ji
2 m&> =
>=i
X m& =
XjZ,)
2>
and
t=i
n
X mi(Vfr 
ziV,)
=0
mfcjXj
=
(3)
=1
204
here
92.
(The separation of vibration from translation and rotation suggested is treated in a more rigorous manner in ref. 1.)
The
of the
is
molecule from
equilibrium configuration.
follows that
displacement coordinates which show the change in the geometry of a molecule from its equilibrium configuration will form a suitable base for a
potentialenergy expression.
of
ways.
changes, Bry, from the equilibrium value of the distances between the
and j.
With
this coordinate
it is sufficient
u =
For
i,i
X =
K(*r)'
l
(4)
H O H',
V=
+ !/c H o(SrVo) + IWOhh') + &HO,H'o(Sr H o)(ar H + kno, (&r ho) (8r Bn + &Ho,HH'(SrH 'o)(5r H H') where the fact that H o = Wo has been recognized.
ik B o(Srao)*
'o)
an'
fc
')
(5)
Such formulations, as Eq. (5), of the potentialenergy function, while complete, are seldom satisfactory. Many more parameters are introduced than can be evaluated, except in favorable cases, from experimental data. Thus, for H 2 there would be four force constant terms in the potentialenergy function, and these ould not be determined from the 3w 6 = 3 fundamental transition frequencies that are observed spectroscopically. It is necessary, therefore, to attempt to
A;,,
find a
way
in
as the molecule
which the change in the potential energy of the molecule is distorted can be described without recourse to this
Two
different
points of view as to the dimensions of the molecule that are most impor
field,
more
frequently used
by
chemists.
The
205
that occurs
when a molecule is distorted from its equilibrium position can best be described by terms in the potentialenergy expression, each of which involves a force constant and a square of an internuclear dis
O
tance.
Thus, for
U=
where
ik B0 (8r B0 )*
+ ikvoiSrn'o) + itHH(5rHH
2
')
(6)
5r H o, 5r H 'o,
and
5r H H' represent
The assumption
i.e.,
fc
number
energy of the
molecule to two,
H o and
A;
H h'.
The valencebond
from
With
this
H2O by
2
the expression
(7)
its
U =
where 8a
i/cHo(5r HO )
is
iMM
HO
like
fc
H o,
will
The two
force
constants k a and
are related
by
k' a
k a /r\.]
As we
band frequencies
can be used to
H2O
deduce values of the constants in the potentialenergy expression. In fact, one can determine the two force constants in the previous potentialenergy expressions so that the calculated frequencies are close to two
of the observed absorption
tial
band
frequencies.
The
by how
When
performed
it is
com
pletely satisfactory.
The
bond
field is
function.
One
can,
if
206
quadratic terms to improve on the simple force fields. Thus one might add a bond stretchingangle bending interaction constant to the simple valencebond potential and write
U =
i&Ho(SrHo) 2
+ ik B
o, a (Sa
(8)
way
in
which the potential energy varies with molecular distortion. Unless, however, one makes use of the spectra of isotopically substituted species,
there
is
no way of verifying
its success.
The
by
determining the force that would act to restore a bond distance or angle to its equilibrium distance. Thus, one might investigate the force
acting to restore the angle between the bonds of
to
its
equilibrium
Restoring force on Sa
ST I
,
k a (8a)
+ %k BO a {8r BO +
,
8r B
>
(9)
One
on angular
seems reasonable, and turns out to be so, that interaction terms, such as k H o, a should generally be small and need not always have
Furthermore,
it
positive signs.
Exercise 91.
NH
Write expressions for the potentialenergy function for on the basis of (a) the simple valencebond force field and (6) the
field.
a diagram showing a displacement of the atoms from their equilibrium positions that would lead molecule 2 to a calculated increase in the potential energy that would be different for the simple valencebond and centralforcefield approximations.
Exercise 92.
Draw
of the
Finally,
it
what
is
called a
UreyBradley
field, is
now
often used
when
fairly simple
This field combines the features of both the and the valencebond field. It has, therefore, terms involving the distortion of chemical bond lengths and angles and also terms depending on the distances between nonbonded atoms.
species can be studied.
207
93.
in
Molecularvibration Problems
The motion
of particles constrained
by
certain forces,
i.e.,
subject
be determined by application of Newton's / = ma relation or, more by Lagrange's equation. In the later method, Lagrange's equation is applied to each coordinate needed to describe the system.
conveniently,
If
a typical coordinate
is q,,
will be, as
we
will see,
3w
6 such equa
6 vibra
tional frequencies
T and U be expressions involving the same set of coordinates. This requirement creates considerable complexity in molecularvibration problems
to set
since, as
we have
it is
convenient
up T in
and
if
internal coordinates,
Rz ne
the coordinates
internuclear distances
which describe the displacements of the atoms from their equilibrium and the bond angles from their equilibrium values,
and the cartesian displacement coordinates are represented by x 3n one usually sets up the expressions
.
xi,
x^,
Sn6
T =
yi
mfbj
(11)
U =
k/RiB,
of course, generally be
(12)
t\j'i
(The values of
& will,
unknown
at the beginning
of the calculation.
They
To proceed from
procedure, as
either the R's in terms of the x's or the x's in terms of the R's.
we
will see
section, is generally
The first when an example is worked out in the following easier to set up since equations of the type
,Xtn)
Ri
fi(Xl,
208
can often be immediately written down. Transformation of Eqs. (11) and (12) to cartesian coordinates, of which there are 3n, leads, however, to 3n equations when Lagrange's equation is applied. In molecules of any complexity it is usually better to obtain, by one means or another,
transformations of the type xs
fj(R h
6 internal coordinates.
will
To
illustrate
be worked out in the following section by this approach. It is true, however, that even 3n 6 equations become difficult to handle, even for fairly small molecules, and
specific
example
by these methods becomes rather troublesome. More systematic ways of handling the problem will be introduced later.
solution
94.
A
tions
is
suitable
HCN, OCS, and so forth, along the axis of the degrees of freedom along this axis will lead to two 3 vibrations, which will involve stretching of the bonds, and one translatype
i.e.,
,
The
The more
example to illustrate the discussion of the previous secthat which considers motion of a linear triatomic molecule of the
molecule.
tion.
differ
only in complexity.
The potential energy is best expressed in terms of changes from the equilibrium values of the distances between the atoms of the molecule.
If the equilibrium bond lengths are denoted by r? and r and changes 2 3 from these values are denoted by dr u and 5r 23 the potential energy can
,
U=
More
nates,
i*i(8n,)*
i/c 2 (Sr 23 )
(13)
generally
we
let
is
displacement coordi,
and
if
we
Ri represent
8r u
and
energy function
written as
U = ihRl + faRl
The
kinetic energy expression can be
If
(14)
x h x 2 and x 3 represent the positions of the three atoms along the onedimensional line of the molecule,
as indicated in Fig. 91, the kinetic energy for the onedimensional prob
T =
frn&l
+ \m x\ + m x
2 3
(15)
209
We
i,
of the
type
x2 x3
(16)
so that the kinetic energy expression of Eq. (15) can be written in terms
of the internal coordinates
.
of coordinates are
related
by the
t
expressions.
(x 2
Br 12
= R = = R2 =
a:,)
r!j 3
r 2
(17)
and
8r i3 (x
x 2)
rg,
(18)
Furthermore, since
rj 2
and
Ri Ri
= =
Xi
x3
ii
(19) (20)
x2
The
R = f(xi
2l
.),
some further effort, as will be seen, is required to obtain the desired expressions which are of the type x = f(RiR 2 .). In the convenient matrix notation, Eqs. (19) and (20) can be written as
are written
typical, while
. .
1
()(
1
Ti
v \x%
X,
(21)
One cannot immediately solve Eqs. (19) and (20), or Eq. (21), for i, x 2 and x 3 in terms of Ri and Ri because of the occurrence of three cartesian coordinates and two internal coordinates. In the matrix expression, one
,
matrix.
The
if
one
no net
linear
momentum
be involved.
FIG.
91.
The
atoms of a
molecule
sional
in
location
of
the
type
moving
onedimen
210
additional relation
ffiiXi
nnxz
miXs
(22)
This expression allows, with Eqs. (19) and (20), or Eq. (21), the expresand x 3 in terms of Ri and ij 2 to be obtained. In matrix
(23)
Now we can take the inverse of the square matrix to get, with the notation
= mi
+m +
2
wi 3
(m 2
'zA
Xi
J
+m
3)
M
3
mi
xj
M
TOl
M
or one can obtain,
M M mi + m M M
2
(24)
by means
Xl
(m 2 mi $
+m
m
3)
Rx
>
m M
_ Ri
(25)
X2
Ki ~M Kl ~M3J
*~M R i+
>
T gives,
after rearrange
ment,
T =
(ml
+ 2m,m,
f
mf ,+
m^Rl
+ 2m m )EiiJ
2
2mim 3
2iim 2
m?
+wm +
2 3
mitn 3 )R
(26)
together with
(27)
U = ihR\ + fan*
211
is
it
to
jp
+
and
2j! (ml
2]^s
2m
+
2
2mi?i
+ 2m m )S + &i#i =
2
3
(28)
2mim 2
m\
(
+ m m + m mi)R\
3
x
+
One can again
Ri
see
if
22^2
2m
2mim 3
+ 2m m )R + k R =
2 3 1 2
(29)
= Ai = A2
cos
2Kvt
( 30)
and
Ri
cos
25tj<<
and
and
2
4*V
(ml
2m 2m 3
m\
+ mm + mm,) + kA
(
Ai
3)
~
and
""
I
4^ 2 " 2
2IJ2
2m l
+ 2wim + 2m m
3 2
A2 =
(31)
47rV
I
Jgp
2m s
(ml
+ 2m m + 2m m
x 3
3)
A,
3
4ttV ^1
+2mim + m? + m 2m
2
+ w^ma) +
ifc
A2 =
Again, nontrivial solutions will exist for the A's only if the determinant of the coefficients is zero. This determinantal equation leads, on expansion, to a quadratic in 2 The two roots of the equation (only
2X2
v)
1/
now perhaps
for
exam
one would know from spectroscopic studies that the frequencies of the absorption bands corresponding to the two stretching modes are 2,089 and 3,312 cm"'. One can now choose numerical
HCN,
values of
tion arising
fc x and k 2 which, when inserted in the determinantal equafrom Eq. (31) along with the values of the atomic masses,
cm".
In this
212
HCN
are
,
= JW =
fc
HC
5.8
32
Exercise 93. Verify that the force constants of Eq. (32) lead, when substituted in Eq. (31), to the observed stretching frequencies of the
HCN
molecule.
Calculate the positions of the absorption bands due to to be expected for DCN. vibrations the stretching
Exercise 94.
Frequently one must make the calculation in this direction, i.e., deduce values of the k's to fit known frequencies. Sometimes, however, one can take force constants from some molecules and carry them over
to other molecules and thereby reduce frequencies from a calculation
of the
It
how a
be considered, vibrates in the vibrational modes that have the frequencies used in the calculation. One needs, therefore, the relative values of A x
and A 2 that solve the set of equations, Eq. (31), when v is 2,089(3 X 10 ) and v is 3,312(3 X 10 10 ) cycles/sec. The relative values of Ai and A 2 and thus the form of the vibrations, can be immediately obtained by (More generally one takes the ratio of the cof acrearranging Eq. (31). formed by the coefficients of the A's.) For the determinant the of tors
,
2,089
cm
A A i
:
0.405
1 .00
(33)
and
For
v
3,312 cm'
A A2 =
x
\
1.00:
is
0.137
(34)
first
is
vibration
predominantly one of
predominantly one of
illustrating
CH
stretching.
the displacements of the Do this by attaching in the two stretching modes. atoms of given to the molecule translation is no net arrows to the atoms suoh that Eqs. given by (33) and (34) are amplitudes relative the that
Exercise 95.
Draw diagrams
HCN
and
so
Deduce relative displacement amplitudes and draw suitable diagrams for the two stretching vibrations of DCN. calculation was Exercise 97. Consider the basis for the fact that some exercises, whereas in two previous the of diagrams the draw to necessary
Exercise 63 the corresponding vibrations of the
CS 2
molecule could be
drawn with
less calculation.
213
The fundamental transitions of the stretching modes of lead to absorption bands at 2,050 and 863 cm 1 If a simple potential function like that of Eq. (19) is assumed, what values of the stretching force constants for the and bonds are calculated?
Exercise 98.
OCS
C=0
C=S
Calculate the relative distortion amplitudes for the two bonds in each vibration, and draw diagrams to represent the nature of the vibrations. Exercise 99. The fundamental stretching mode transitions of the C0
2
molecule correspond to frequencies of 1,388 and 2,349 cm 1 (the former is not infrared active). By the procedure outlined in Sec. 94, obtain a value for the force constant from these data (a) on the basis of a potential function like that of Eq. (13) and (6) on the basis of a potential function that includes a cross term between the two bonds of the
C=0
molecule.
i.e.,
solution for the stretching modes of a in internal coordinates, illustrate the proIt
is considered, the solution will require the imposition of zero angular momentum as well as zero linear momentum. Thus one imposes, in the general
case,
the conditions of Eqs. (2) and (3). It should be apparent from the simple example treated here that the analysis of the vibrations of a molecule with many atoms will involve the solution of equations of high order.
This
is
particularly troublesome
when
force constants Considerable simplification results, fortumolecules have elements of symmetry. Some of these
frequencies
features will
95.
now be
considered.
in
Use of Symmetry
Vibrational Problems
of the relation between the force constants and the vibrational frequencies of all but the simplest molecules is frequently
The determination
from the symmetry vibrational problem of benzene involves 3w  6 = 30 internal coordinates, and one would be led to a 30 X 30 determinant of the type that would arise from Eq. On the other hand, if full use is made of the symmetry of the (31). benzene molecule, the problem factors down to one 4 X 4, one 3 X 3, and several 2 X 2 and 1 X 1 determinants. The calculation is then perfectly feasible.
feasible only when the simplifications that result of the molecule are recognized. For example, the
The
symmetry introduces
is,
as
2U
mentioned
of
symmetry
coordinates.
The com
if
binations are such that each symmetry coordinate is symmetric or antisymmetric with respect to each symmetry operation. One recalls that and S are symmetry coordinates that behave differently with respect
to
any symmetry operation, perhaps Si > S, and S p occur must not S S term cross the P ticular operation, then
> {
Si
Sp
in
for a par
T and
a term
S SP symmetry operation would convert SiSp * <,< and SiSp SiSp and This molecule. the of energies potential the would alter the kinetic and symmetry 64 that a in Sec. reached conclusion would be contrary to the
involving
(
If
operation cannot result in any change of the kinetic or potential energy The effect of the absence of cross terms between elements of a molecule.
of different
symmetry types means that the determinant resulting from will application of Lagrange's equation to the symmetry coordinates
have blocks of zeros in the offdiagonal positions that correspond to the Thus crossterm positions between the different symmetry coordinates.
the determinant has the form
a
o
o
=
a
o
(35)
be a subdeterminant of order equal to the number of coordinates of that symmetry type. Since the total determieach nant will be zero if the determinant of any diagonal block is zero, vibrational block can be set equal to zero and can be solved for the
will
frequencies of that
symmetry
is
determinants to be solved
benzene, of high
This reduction in the order of the very great in the case of molecules, such as
type.
symmetry.
The use
of the
symmetry coordinates can be illustrated by the example problem can molecule. The 3n  6 = 3 internalcoordinate
of
215
be expected to reduce, according to the discussion of Sec. 813, to one involving two totally symmetric coordinates, of type A and one antih symmetric coordinate, of type B 2
.
We consider the H
,
we
set
up coordinates
which not only have the symmetry appropriate to the normal coordinates, i.e., two Aj and one B 2 but also are such that they involve no translation
or rotation of the molecule.
grammatically
in Fig.
92
by the three
figures.
The proper
relative
lengths of the arrows in each figure can.be designated by indicating that displacement according to Sj consists of motion of and H' by Si units
shown; displacement according to S 2 consists of motions of H and H' by S 2 units; and by 2mu/m units as shown; and so forth. The relative atomic motions that constitute S S 2 and S 3 are then h compatible with the symmetry requirements and involve no translation
,
in the directions
These coordinates are convenient for solving the vibrational H 2 type molecule. Again one must write the expressions for T and U in the coordinates in which they can be immediately formulated. We can write, for motion
or rotation.
problem
of the
T = im B (xl
and
2/)
tf.)
(36)
U=
PoH(5r OH ) 2
(37)
2m H
*2
S2
FIG. 92
molecule.
216
Now
and Sr necessary to have the coordinates x B #h, <S 2 and S s so that we can obtain
,
. .
.
a,
T =
and
t(Si,S h S 3 )
(38)
U=
u(Si,St,S t )
(39)
It is first
necessary to ask
,
how
metry coordinates Si, S t and <S 3 can lead to motions of the atoms equivInspection of Fig. 92 allows one to write alent to xs, j/h, and so forth. immediately the velocities that the atoms would have along the cartesian directions in terms of velocity contributions based on the symmetry
coordinates as
xB
= =
a Si
Si
Si sin a; x
cos a; y
= =
2m H <S
***
sin
a
;
= Xw _
2
*
<!>i
S3
sin
a
(40)
too
'
;
Vh
 S
V*'
= S + S3
cos a
T = m*S\
The
+ m H (l + ^) SI + m H (l +
sin'
a) Sj
(41)
between the internal coordinates and the symmetry coordinates can best be found by first writing the cartesian displacements Thus of the atoms that result in bond stretching and angle bending.
relation
8f 0H 8r
OH
= =
(dXo
&Xn) sin
(Sy
(dy Q
J/h)
(dXo
J
Sxw) sin a
+
a
(42)
=The
(Sxw
Sxk) cos
({/h<
2j/
sin
expressions for the effect of changes in the symmetry coordinates on the cartesian displacements, written in Eq. (40) for the time element dt, can be used to convert Eqs. (42) to the desired relations
5r 0H
= = 
sin
S 1
cos a (l cos a (l
+ ^) S, + (l + + ^) S, +
(l
6r OH,
sin
aSi aSi
=  cos
+  sin
a (l
^ +^
sin2
) Si
sin*
a) S 3
(43)
sin a")
S2
and These transformation equations between internal coordinates given V symmetry coordinates can be substituted into the expression for
217
u
'
k BO sin 2 a
~
r
.
2fe,
cos 2 a
S%
J
,
'2
+
+
,
fc
. HO cos 2
A 2m H \ ^l+ j
a cos \
+71
Wo /
2ka 
sin2
H \ 1 (\ __ ^i + 2m smajjs
2
,
2A; H o sin
4A;
5
sin
a cos a
(l+^o.)]"'
+
Now
of the
that T and C/ are expressed, by Eqs. (41) and (44), in terms symmetry coordinates S h Si, and S h Lagrange's equation can
and
solutions of the
2irrf
form
Si
Si Sz
Ai = Ai A
z
cos
(45)
can be sought.
if
Nontrivial solutions of this form are then seen to exist the determinant composed of the coefficients of the A's is zero. The elements of the determinant are rather cumbersome, and it is
T =
and
a n &l
a 22 Sl
+ owSj
l(
(46)
U =
where the
buS{
+ 2&
12
S2
6 22 SI
b n Sl
(47)
a's and b's refer to the coefficients of the terms of Eqs. (41) and (44). Furthermore, the customary procedure of designating the term 4irV by X will be followed, and this leads to expressions comparable with those shown as Eq. (31) in the internal coordinate treatment of Sec. 94. The determinant of the coefficients of the amplitudes A h A h and A 3 is set equal to zero to give the equation
6u
Xan
621
612 622
Xfl 22
=
&33
(48)
X<l33
It is clear
that the
down
of the 3
3 determinant
toa2X2andalXl
The two
218
from expansion
2 subdeterminant.
On
I
2

8bl2
(49)
anffl2 2
a 2 2/
third root of the determinantal equation, corresponding to the antisymmetric coordinate, is seen immediately to be X = 633/033
The
type molecule
bond
angle,
and
For the
molecule, for
O bonds has been determined example, the angle between the two One can then verify that the force constants to be 105 deg.
fcno
7.76
10 6
and
0.69
10 5
dynes/cm
the lead to the calculation of frequencies in quite good agreement with 1 and modes observed values of 3,652 and 1,595 cm" for the symmetric
3,756
cm1
mode.
The form of each of the three normal coordinates can now be determined. One of the roots of Eq. (48) is substituted into the determinant,
and
for this value of X, or
v,
is
calculated.
When
this is
modes can be described by linear combinations of Si and antisymmetric normal coordinate is, apart from a constant ing other than the antisymmetric symmetry coordinate <S 3
.
Exercise 910.
99,
method
of
symmetry coordinates
Problems
in
Internal Coordinates
by the
Method
of Wilson
The treatment illustrated in the previous section can be systematized by an approach introduced by E. B. Wilson [J. Chem. Phys., 9 76 (1941)].
:
This procedure
vibrations
is
many
of
Wilson will will be approach Additional material on this therefore be elaborated. depends procedure found in ref. 1. It should be pointed out that the on a familiarity with matrix methods.
now
being done.
The
original presentation of
sets
up both the
kinetic
219
Rk
out, the
and one
2U = ^k R k R
kl
kl
will
The notation used by Wilson designates the now follow this notation and write
force constants
by /.
We
2U = ^fhiR k Ri
kl
or, in
matrix notation,
(50)
W = R'FR
where R'
is
the transpose of R.
The
may be
clarified
if
the par
problem studied in
up
Thus Eq.
can be written as
is
recognized to be
\0
ki)
set
To
up the
3n
must
2T =
It is
m<x\
(51)
defining
convenient to absorb the mass coefficients into the coordinates by new coordinates g( that are proportional to the cartesian coordi
them by
(52)
(mi)ixi
With
23
= I t=i
in the
(53)
As we saw
94, the
time
set
are related
by a
220
1=1
or, in
matrix form,
(55)
R = Bx
where
with
is
6 rows, x
is
a column matrix
3ft
rows, and
is
of the
example
molecule.
The
which
appropriate to the
(f)
problem.]
The
the
<ji
coordinates, are
3n
Rh =
and
J)
D Mq\
where
D =B
ki
ki
(m,) _i
(56)
=i
R = Dq
The
principal problem
now
is
to proceed from
2T =
1
t=i
mi%\
i=i
9l
R = Dq
to an expression for
sion for
is
(57)
in
terms of
that
is
in terms of
necessary to impose the conditions of zero translation and zero angular momentum so that, in effect, the inverse transformation of Eq. (57) can
be found and inserted into the kinetic energy expression. can be made square by writing, as six additional The matrix rows, the six conditions of zero translational and zero angular momentum.
In this
way
the matrix
2D
where
(58)
= (.)
221
ar = (QQ
1
(59)
where and 2D are square 3w X 3n matrices. Furthermore, D 1 has been arbitrarily divided into Q, a 3n X 3w 6 matrix, and Q a 3n X 6
,
1
matrix.
(Note that
depends on both
3>,
and
as also does
.)
one has
(60)
>g
where
as q
r = I>o9 is a column matrix consisting of six zero elements. Now the desired inverse of Eq. (60) can, formally, be written down
SCr'CR
(62)
With
as
can express
2T =
q'q
^'(XrO'SCr 1 ^
(63)
6,
dimensions.
Since
"(f)
and
and and
'
= =
(#'r')
(64)
GO
 =
1
SLV
(O'i>'o)
(65)
(QQo)
(ori) '
to/ = (S)
(66)
2T
can be expanded as
2T = IT 
(R'r')
(<Q
(QQ a) (f)
(67)
(R'Q'
=
Since r
is
ii'Q'QB
(68)
a zero matrix, the last three terms are zero and one
with
(69)
2T = R'Q'QR
The
deduced.
desired reduction to
It
3n
6 matrices has
the matrix
now been
formally
accomplished.
remains to see
how
can be conveniently
222
The matrix Q
useful relationships
matrix 2X
number
of
become apparent
if
one writes
ST 1 = (QQ
and
(\ =
{QD
QoDo)
J 3 X 3
(70)
wr> = ()
venient in that
of the
it
> 
( S%) =
'
<
71)
3n
3m 3n
6 X 3n matrix D i.e., 3n 6 rows and 3n columns, and the  6 matrix Q, is a 3w 6 X 3n 6 identity matrix. The first
now be made
to yield a valuable result.
It is first
relation can
transposed
to give
D'Q'
D' Q'
7 3 X 3
left
(72)
by
and on the
an
right
by Q
to give
(73)
DD'Q'Q
DD' Q' Q = DQ = 7 3 6 X
6
Now
one must recognize that the internal coordinates will be the basis
D and D
and that DD' is a zero matrix. term of Eq. (73) and leaves
DD'Q'Q = I
The product Q'Q
Q'Q =
desired for
1
(74)
is
then obtained as
(75)
(DDT* = G
important matrix.
where the usually used symbol G = DD' has been introduced for this In view of the relation between the components of D and B given in Eq. (56), one can express the elements of G = DD' as
an
Q =
From
2,^
we can
.
.
(76)
this result
G
6.
matrix,
i.e.,
Gki
for k
1, 2,
3n
6 and
1, 2,
3n
(It will
be
223
internal coordinates
is the transformation matrix between the and the cartesian coordinates and that it can b e written down from a consideration of a diagram of the molecule.) One now has
matrix
2T = R'G'R
and
2*7
(77)
= R'FR
is
(78)
When
Lagrange's equation
vibrationaltype solutions
Rh = A k
A k 's
cos 2rvt
formed by the
coefficients Of the
Fu F 
(6)iiX
((? 1 ) 2 iX
F ^22
(G^OiiX
(G'UX
(79)
where X = 47rV. If A is used to represent a diagonal matrix with on the diagonals, this equation can be written as
\F Finally,
X's
ffA
=
\G\
(80)
it is
multiplying through by
\G\ \F
GiA
= =
\(G)(F
A
(7A)
\GF
(81)
With either Eq. (80) or (81), and the procedure obtained for setting up the F and G matrices, we can solve for the 3w 6 values of X that molecular type example can be satisfy the equation. The used to illustrate Eq. (80) or (81). In more complicated cases the systematic nature of "Wilson's FG method" is of real value. Probably
most of the molecularvibration calculations that have been published have made use of this procedure.
'"Exercise 911. Calculate the frequencies of the the given force constants, by the method of Sec. 96.
*97.
HCN
molecule, from
Formation of the
is
presented.
The
224
e* = /
where the
ZT BkiBli
terms that
k,
1,
3n
(82)
ki
arise are
3ra
Rk
i=l
B*A
(83)
It is
now
more
specifically to
show Eq.
(83) in the
4i ,gi)
form
Rk
(B kXl i
B^yt
+ + +
These
(B kXl xt (B kXn x n
+B
kVl
+B y +
2
+ B kyJ n + B
kz J)
many
with components x
t,
y,,
zt
and
sjtt
with components
B kx B ky B
kZl
where
numbers
off
With
this notation
Rk
is
written as
Rk = ^
<
s*t
p(
(84)
=i
(?*!=> bm
ti
(85)
Gu can
its
and recognizing
Gkt
as
(86)
(79),
This
is
s*t
su
(B
lXl
+B
zt
ky ,Bi Vl
+ B/c^Bu,)
i.
is
except for
y
is
t,
The
helpful only
is
a convenient
way of
e a/s
The
subscripts a
and
/3
indicate
225
it is
With
these
possible to set
up convenient
recipes for
determining and
vectors,
i.e.,
atom
(to a particular internal coordinate Rk. If Rk involves the stretching of a bond, say between atoms labeled a and /3, the s* a and s^ vectors must show how the terminal atoms must move to lead to a bond stretching.
In this
Ska
= 6<*0
(87)
and
Thus
if
molecule
one were dealing with the internal coordinate Ri = H O H' and the vector had been indicated as
Sr on for the
H
one would have
/
H'
and
SlO
(88)
BO
Rk involves an angle bending, Sa for H 2 0, for example, one draw the e vectors directed away from the apex angle thus
If
agrees to
e OH//
WCoh'
More
generally, one
fix
the value
vectors as
226
Furthermore one lets r 3i and r 32 denote the equilibrium bond lengths and <p the equilibrium value of the interbond angle. Some geometric
manipulation
is
now
show how, in terms of the vectors, the three atoms must move to in an increase in the angle with no accompanying bond stretching. finds that, if R k is an angle bending coordinate,
S*l
One
_ = =
cos
y> 31
:
<p
t 32
sin
:
(89)
c3i
cos ye 3 2
<p
,.
S*2
r 32 sin
(r 3 i
(90)
r 32 cos *>)!
Sk3
+ On

cos
<p)e 3 2
nn mji
,
r 31 r 8 2 sin
<p
s vectors
and the
ducing the molecular geometry into the problem, allow, for very
many
G matrix elements to
expression
= 7 G "'= ?w 7
ZT s
e
*<
s"
92 )
way
cosines of angles
between bonds
and
will, in
into the
matrix.
Exercise 912. Apply the Wilson FG method to the molecule HOD. Calculate the frequencies predicted on the basis of the force constants kno = k D9 = 7.76 X 10 6 dynes/cm and lc a /r 0H = 0.69 X 10 5 dynes/cm. Compare with the observed absorption band frequencies of 1,402, 2,719,
in
Wilson's
Method
It
has already been shown, in Sec. 95, that the use of symmetry
coordinates, which can be expressed as linear combinations of internal coordinates, allow the secular determinant to be factored into a
of determinants of lower order.
number
two
Si
can be
set
up
in
227
coordinates Rk according to
3JI6
S =
t
^ U R
lk
(93)
=i
(94)
or
8 =
For
UR
5ri
H
S,
= = S3 =
(S 2
5r 2
Sa
Sr%
8r 2
(95)
or
0\ /r,\
1
)(*)
(96)
1
Since, as Jhis
0/\5a/
illustrates,
example
will
the
up
relation,
l7i
which
be used below,
(97)
U'
will hold.
is
expressed as
(98)
2T = R'GiR
The corresponding expression involving symmetry coordinates can be obtained by inserting the identity matrices UU 1 and C/_1 C7 to give
2T =
R'UWG^UWR
is
(99)
Now UR
R'U'
is
recognized as S'.
U~ =
l
U',
we can
l
write
(100)
2T = S'UGWS = S'& S
where the notation
gi
UGW
Since
all
(101)
= (/')= UGU'
W
(102)
This matrix equation allows, since U and are known from the way in which the symmetry coordinates were set up and the elements of G
228
can be calculated from Eq. (92), the calculation of Eq. (102) shows that the elements of 8 are given by
7i
Expansion of
3n6
u,kUi,h
1
'
s "'
2 (i X
kik'=
akt
sk
(103)
This cumbersome expression can be used more conveniently if symmetry displacement vectors S\ that are comparable to the s k t vectors are introduced..
If Sj is defined as
3n6
S= I Uun* 4=
1
(104)
8 ,
= ^iSSS
i=i
(105)
With Eqs.
(104)
of Eqs. (100)
and
Thus one
stitutes these, along with the appropriate atomicmass terms in Eq. (105), to obtain the desired kineticenergy matrix based on the symmetry
The
energy expression
217
= R'FR
(106)
internal coordinate matrices R and R' can be replaced by symmetry coordinate matrices by use of the relations, obtained from Eq. (94), and
The
R = uW =
and
R'U'
U'S
1
(107)
= R'U =
S'
or
R'
= S'U
(108)
2U = S'UFU'S
or
(109)
217
S'5S
(n)
229
'S
= UFU'
(100)
(111)
With Eqs.
and
(110)
for obtaining
g and
ff
can be analyzed in terms of symmetry coordinates and, as seen in Sec. 95, the convenient factoring of the secular determinant will occur.
Apply the Wilson FG method, making use of symmetry S0 2 molecule. The molecule is bent and has a bond angle of 120 deg. The force, constants reported for a simple 6 valence force field are k a0 = 9.97 X 10 6 dynes/cm and k' a = 0.81 X 10 dynes/cm. (Compare with the observed frequencies of 519, 1,150, and
*Exercise 913.
as indicated in Sec. 98, to the
1,360
cm
.)
PRINCIPAL REFERENCES
1.
Wilson, E. B.,
Jr., J.
New
York, 1955.
10 I^^V
ELECTRONIC SPECTRA
OF DIATOMIC MOLECULES
Molecules can absorb, or emit, radiation not only as a result of changes in their rotational and /ibrational energies but also as a result of changes
in their electronic
arrangement and, therefore, their electronic energy. The energy changes involved in a transition from one electronic state
of a molecule to another are usually relatively large
and correspond to
it
We
broad absorption
or emission bands
structure.
large
amount
of fine
tion on the
moments
for the
many
deduced from studies of electronic transitions. The lack of a simple, generally adopted pattern for the energies of these excited states makes, as we will see, the assignment of transitions to For only a few particular states a problem of considerable difficulty.
of these states can also be
be drawn.
The
that
230
is
analysis of electronic
bands
of diatomic molecules is
perhaps
Follow
best introduced
by considering the
vibrational
found
231
can occur for a particular molecule mention will be made of how an observed band can be will be given, and assigned to a transition between two of these states.
of the kinds of electronic states that
It
Much
We
and
will
for those
make reference to the very complete treatment given in ref. 2 who wish to pursue further the detailed study of the electronic
in which the potential energy of a diatomic molecule might vary, as a function of the internuclear distance for two different
The way
i.e.,
two
different electronic
on such diagrams and with various shapes for the different electronic states of a particular molecule. The curves shown in Fig. 101 are, however, typical of a ground and an excited electronic state. The potentialenergy curves of Fig. 101 imply that for each of the two electronic arrangements the molecule will vibrate, and, as in Chap. 2, horizontal lines are drawn to represent the energies
in Fig. 101.
will see later that
shown
We
molecule being found at various internuclear distances, i.e., the square of the harmonic oscillator wave functions, are shown on the energy
levels to
which they
will
refer.
We
now
changes the molecule from one electronic state to the other. The question immediately arises as to which transitions are to be expected between the various vibrational levels, labeled v" = 0, 1, 2, of the
.
. .
v'
0,
2,
of the
upper electronic
question.
state.
in
232
FIG. 101
ability functions
^2
for
two
a diatomic molecule.
Internuclear distance
*
233
transition going
no general restrictions on the changes in v for a from one electronic state to another. This result is in
= +1
that
is
It
must be kept
in
mind that
electrons can
move and
rearrange
themselves
much
faster
(The relative times for electronic and nuclear motion can be recognized, for instance, from the fact that an electron in a Bohr orbit of an atom completes a revolution around the nucleus in about 10 16 sec whereas a typical molecule vibrates with a period of about
nuclear distance.
10"" 13 sec.)
compared
to the vibrational
can be regarded as fixed during the transition. follows that on a diagram, such as that of Fig. 101, electronic transitions
must be represented by essentially vertical lines connecting the initial and final states at some fixed internuclear distance. 3. The fact that the probability of the molecule being at a particular internuclear distance is a function of the distance, as shown by the probability curves of Fig. 101, must be taken into account. An electronic transition must be expected, in view of the transition moment integral defined in Eq. (425), to be most favored if it occurs while the molecule has an internuclear distance such that the transition connects
probable states of the molecule.
This rule
is
level
in Fig. 101, by conmore probable if they begin or end or either end of any of the higher vi
shown
brational levels.
With
is
done in Fig.
often near
102,
is
room
level is
most populated.
One
expects,
band due to
and
v'
to large values.
CO
and
I2
which
Exercise 101.
Draw
spectrum of upper
observed.
234
is
many
levels,
of the
v'
In emission spectra,
state
therefore,
many
i.e.,
various
various v"
The many probable transitions that occur such complexity, as that of the molecule N^ shown in Fig. 104, that without considerable experience one cannot recognize how the band structure is related to transitions such as those
values, are to be expected.
generally lead to a
band
of
band
way
approximately constant
and varies uniformly, and the difference in the frequencies in adjacent rows is likewise approximately constant and varies uniformly. The
FIG. 102
relatively
(o)
Some of
Examples
electronic
between vibrational
levels of
two
(Note, as Table 101 shows, that for a given value of v transitions to states with
two
235
components of an electronic emission band of the molecule PN, arranged to conform to these requirements, as shown by the frequency differences also exhibited, are given in Table 101. This pattern is understandable in terms of the emission transitions of Fig. 1026 if the columns
are labeled with the vibrational
tronic state
state.
quantum number v" of the lower elecrows with the quantum numbers v' of the upper
in the table can then be identified as a transiit
column.
The most
curve as would be expected from the potential curves of Fig. 101 and the three statements given earlier in this section. For v' = 6, for example, preferred transitions are apparently those going to v" = 3 and
boliclike
v"
9 or 10.
Thus
v'
two
The
rows of the Deslandres table can now be recognized as giving the spacing of the vibrational levels in the upper electronic state, while the differences between the values in the columns give the vibrational spacing
in the lower electronic state.
It
should
now be
clear that
than can be obtained from direct One obtains information on the enerstudies of vibrational transitions. gies of levels with high vibrational quantum numbers, and one can learn, therefore, much about the potentialenergy function. For example, there
level pattern of a diatomic molecule
is
2,000
an electronic transition of I 2 that leads to an absorption band at about A connecting the ground electronic state with an excited state. The vibrational structure of this band has been measured in considerable
and transitions involving groundstate vibrational quantum numup to v" = 114 have been reported. From the data on these vibrational spacings, some of which are summarized in Table 102, a This is shown welldefined potential energy function can be deduced. in Fig. 105 along with, for comparison, the Morse curve that was introduced in Sec. 23. (The Morse curve is generally accepted as a good
detail,
bers
approximation to the potential function of a diatomic molecule.) In favorable cases, such as the I 2 transition mentioned in the previous paragraph, the pattern of vibrational levels almost up to the limit of dissociation can be obtained, and the dissociation energy for the molecule
in that electronic state
<k
O S
8
8
o
o
>!
X
7
1
j
io
1
1 o (3
o m
o". u
3
to
ja
o
t
*
,
2
4
O
_g
z
C C C
+
JQ
a,
<3
.2
Kl2
P
.F=
I
2
LI
03
O
I
* E o
<
u_ Ji _Q
236
BeS 3UOJp33
jaddf)
J3AU)
J
'
S08E
IS
**
to
LLS'%
SSI'E
Of
S* D
e i
<
i
4)
^
O 6
(j
S
ZZ6Z
II
og
^ w N
ii
n *
o
H C
O rr
a)
e
237
238
also, in contrast to studies in the infrared region, for excited electronic states. (Some molecules have been studied sufficiently so that a rather detailed diagram
of potential
An example
Bands
an electronic band
is
it is
studied with a spectrograph with sufficiently observed that each of the vibrational com
ponents, studied in the previous section, does not consist of a single line but is rather a subband of considerable detail. This additional detail can be attributed to changes in the rotational energy of the molecule
component
of
an electronic
and l'j the rotational energy of the molecule and the /" rotational state, the rotational
TABLE 101
in
)eslandres
X
39,698.8
(1087.4)
1
(1322.3)
38,476.5
(1090.7)
(1307.5)
37,068.7
(1086.8)
40,786.2
(1072.9)
(1319.0)
39,467.2
(1069.0)
(1311.7)
38,155.5
(1294.2)
36,861.3
(1071.6)
41, 859'.
(1322.9)
40,536.2
(1061.2)
37,932.9
(1280.4)
41,597.4
(1309.1)
40,288.3
(1042.9)
4
S
41,331.2
41,066.1
(1015.9)
42,082.0
7 8
9
From
_G.
239
details of the
in
= h+
e'J)
(It should be mentioned that, particularly in studies of the rotational and vibrational structure of electronic bands, use is generally made of a different notation than has been used here to designate the various types
can have.
energy,
i.e.,
if it
minimum
The symbol G
is
molecule, while
represents
used to represent the vibrational energy of the Finally, a double its rotational energy.
prime represents a lower energy state; a single prime, a higher energy Since detailed analyses of electronic bands will not be given here, state.
it
not be necessary to change over to this standard notation.) Although many excited electronic states have electronic angular momentum contributions that couple with the rotational angular momenwill
tum
of the molecule,
it is
here
Table*
cm 1
36,662.5
(1060.0)
(1265.3)
35,387.2
(1059.2)
37,712.5
(1043.9)
(1266.1)
36,446.4
(1252.4)
35,194.0
(1042.6)
38,756.4
36,236.6
(1238.3)
34,998.3
(1029.4)
38,519.4
36,027.7
(1225.5)
41,798.3
41,522.6 41,239.4
240
for the
two
by the
expressions.
?
5.
B'J'{J'
1)
B' V 'J"(J"
1)
(2)
B"
and
tions in which
&J =
0,
on J depend on the types of electronic However, one frequently has situa+1 are allowed. For these rotational branches
is
one has,
if
the value of
J"
simply labeled as /,
1
branch: J"
v
J, J'
= J (B' v
;,
=
J, J'
+ B' ')J +
V
{B' v
B' V')J*
branch: J"
i>
= J
c:
= h
B'j)j
(5;
b;')/ 2
(3)
TABLE 102
Some of
ObA*
Ai (cm" 1 )
213.31
10
11
200.68
40
41
154.62
60
61
110.09
80
81
52.33
9.0
0.5
From R. D. Verma,
J.
241
branch: J"
v
J, J'
= J
+

;,
25:
(35;
5:')./
(B' v
2 B' V')J
These expressions are similar to those encountered in Chap. 7 where vibrationrotation bands were treated. There, it will be recalled,
was a good approximation to set the B values for the different vibra B"). tional states equal and to neglect the terms equivalent to (B' v
it
apparent when the rotational structure of vibrationalelectronic transitions are analyzed is that B' v and B", can lengths, be very the bond and therefore the moments of inertia and
The
is
The potentialenergy curve for the ground electronic state of h. The solid computed from the vibrational energy levels deduced from an electronic emission [From band that is observed at about 2,000 A. The dashed line is a Morse curve for 2 R. D. Verma, J. Chem. Phys., 32: 738 (I960).]
FIG. 105
is
line
12,000
10,000
8,000
6,000
4,000
2,000
242
bond
lengths.)
It follows
J 2 term
of Eqs. (3)
components of the P and R branches will not, therefore, move out linearly from the band origin. In fact, if, for example, B' is greater than 8", the J 2 terms of the P branch can, at high J values, dominate the terms linear in J and the branch components will "turn around" and move to
higher, instead of lower, frequencies as
.7
increases.
Similarly,
if
B'J is
the linear
J components
of the
shown
com
A large difference in B[ and B'J has the shown by the second of Eqs. (3), of spreading out the Q branch components and thereby preventing the sharp Q branch that is often a dominant feature of vibrationrotation spectra. A vibrational component of an electronic transition of CuH, for which the rotational selection rule is A^ = 1, is shown in Fig. 107, The components of the branches of such bands are usually sorted out, and
ponent of an electronic band.
further effect, as
this is particularly necessary
when
the branch
is
overlapped or forms a
band head and moves back on itself, by plotting the line frequencies against a quantum number, as shown for the v' = 0, 0, i.e., v" = band of a CN transition in Fig. 108. The parabolic behavior that is to be expected on the basis of Eqs. (3) is then observed, and the assignment
of
made
fall
is
on a
first
recognized
by Fort rat,
now
apparent
Insfjfufe
lines o( Fig.
Enlargement of a component of the emission bond of Ns showing thot the 104 are in fact band heads. {Courtesy of J. A. Marquises, Cose
3,805 A
243
/j 9
Rn
Kl3
FIG. 107
The rotational
fine structure of
4.280A.
H. GoHrrow; Z. Physik,
Eqs.
(3),
and B"
for the
two
states
In this
way one
equilibrium bond lengths not only for the ground but also for various
Fortrot
parabola formed by plotting the frequencies of the rotational lines against the rotational quantum number in the lower
(From G. Herzberg, "Spectra of Diatomic Mofecules," D. Van
1950.)
energy electronic
Nostrand Company,
L
25,740
_i_
_L
80
J_
25,800
J_
20
J_
25,900
60
40
jj(cm
)
60
80
10
40
244
an accuracy comparable to that provided by direct studies of rotational transitions in the microwave region. It has now been shown how typical electronic bands of diatomic molecules can be analyzed to yield information both on the shape of the potentialenergy curve, as a function of the internuclear distance, and on
the internuclear distance at the
i.e.,
minimum
of a diatomic molecule.
now
necessary to see
if
an electronic transition can, in some way, be characterized. When this can be done, the potentialenergy functions can be assigned to particular electronic arrangements and a vast amount of information on molecular bonding is made available. It is essential for the chemist, if he is to have access to this information, to learn something of the notation, and the implications of the notation, used to describe electronic states. The remainder of the chapter will be devoted primarily to this
in
end.
The material
of Sec.
104
is,
that the molecular orbitals discussed there will be used again in connection with studies of the electronic states of polyatomic molecules in the
following chapter.
103. Electronic States of
Atoms
of
A review of some features of the way in which the electronic states atoms are described is necessary before the corresponding descriptions
Application of the Schrodinger equation to a hydrogenlike atom,
i.e.,
fied
n
I
= =
1, 2, 3,
principal
,
quantum number
p, d,
.
0,'l, 2,
(or
s,
.)
angular
momentum
quantum number
and
m= +
I,
1,
0,
+1
An
atom
is
defined, that
is,
the energy
and probability function for the electron are given, by values for the Furthermore, as application of the approprithree quantum numbers.
ate operator
of the
quantum number
implies an
245
orbital angular
momentum
of \/l{l
l)'(fc/2ir)
of the
of
quantum number
momentum
This procedure for describing the electronic state of a oneelectron system in terms of quantum numbers can be extended to atoms, or ions, consisting of one electron outside one or more filled inner shells by using
an
By
such an
and spatial
lost.
The energy
of the outer
electron
This is shown scheI as well as on n. can be shown, however (see, for example, H. Eyring, J. Walter, and G. E. Kimball, "Quantum Chemistry," pp. 124143, John Wiley & Sons, Inc., New York, 1944), that, since
becomes dependent on
It
and
no angular
momentum
I
momentum
implications of
p,
and d
orbits,
an outer electron are not destroyed. The and magnetic quantum numbers m for the which are important in spectroscopic studies, are shown
and
in
Fig. 1010.
With the
theoretically
result that
momenta
quantum numbers
and
FIG. 109
on the allowed
= 4
tn
* 3^
One
electron
Af
Ad
Ap
4
3d 3p
3*
= 2
=l
atom
Is
246
to describe
atoms
in
terms of their
if
for the
assumed to behave relatively independently, one can begin to describe an electronic state by assigning each outer electron to an available electron orbit; i.e., one can assign values of n, I, and m
are
moment they
FIG. 1010
like the
s,
p,
and d
orbitals.
Note
that, rather
field direction is
greater the more the orbital projects out from the axis
Symbol
z
r
Angular momentum
in
;=2
m = l
^g
m=
<
J3r
mJCw
m=l
m=
m=
247
quantum number
+i or ,
two electrons to be assigned identical values of n, I, and m. One would indicate the ground state of the oxygen atom, for example, by
[<U)](2a)(2p,)(2p,)i(2p,y
The number
of electrons in each orbit is indicated by the superscript, and as is customary, the inner closed shells are set off with brackets. Such an abbreviation, giving a description of an electronic state in terms of the orbitals occupied by the individual electrons, is said to specify
we
will see
that the writing of an electronic configuration can also be the in describing an electronic state of a molecule.)
first
step
Exercise 102.
fluorine
tions
atom and for the phosphorus atom. Suggest electron of these two atoms that would correspond to excited
states.
For an actual atom, or molecule, however, the supposition that the It is not even clear what is meant by the contribution of the individual electrons of the atom when they interact with each other to give some net effect. It turns out,
electrons are noninter acting cannot be made.
however, as can be seen from a rather lengthy quantummechanical argument (see, for example, Eyring, Walter, and Kimball, "Quantum Chemistry," chap. 9), which need not be given here, that the electronic
an atom is determined, in part, by the quantum number L which is the counterpart of the individual electron quantum number I. (The effect of a magnetic field on a manyelectron atom will be treated later, and then the counterpart of the individual electron quantum numstate of
ber m will be introduced.) The quantummechanical treatment further shows that there is a simple relation between the values of /, of the individual, presumed noninteracting outer electrons and the values of L for the atom as a whole. The possible electronic states, for example, of an atom with two outer electrons in orbits with quantum numbers h and l 2 are described by values of L calculated according to
,
L = h
If
h,
U 
1,
2,
(h
l t)
L are
L =
2, 1,
orO
248
In the same
. . .
way
s,
p, d,
to indicate
.
.
values of
0, 1, 2,
one uses S, P, D, to indicate L = 0, For the present example with two p electrons one would 1, 2, ... designate the electronic states corresponding to L = 0, 1, or 2 by the
for individual electrons,
. .
Although the fact that the two electrons are p elecp and one d, is of primary importance in determining the energy of the electronic state, the way in which the two electrons are arranged in the p orbitals, i.e., the value of L, has some
letters S,
P, or D.
configuration
different energies.
The
but
can be deduced from spectroscopic studies. The net electron spin of the atomic state is described by a quantum number S and, again, this atomic quantity can be deduced from the spins
of the individual outer electrons.
that
S can have S =
Si
s2
or
S =
Si
s2
have
S =
for a
or
S =
state of an atom, with a given electron dependent on the net electron spin. Exact calculations of the relative energies of states with different net spins cannot be made. There is, however, a general rule formulated by Hund, which
configuration,
also
states
at
it would be expected that states with <S = 1 would have lower energies than those with S 0. This rule can be easily remembered in terms of the obvious electron repulsion and, therefore, increased energy that would set in if, for example, two electrons were paired up in a single p orbital. If they occupy different p orbitals, the repulsion will be much less. For the former case the spins must be
paired,
i.e.,
<S
0,
and
may
be
parallel,
i.e.,
S =
1.
In spectroscopy
angular
it is
momentum
I
implications of the
S.
momentum
of \/l(l
momen
249
turn of
\/L(L
the atom.
Further
more,
momentum
of i(h/2ir)
on
momentum
of S(h/2ir).
Instead of using the previous equations to deduce the possible values of the quantum numbers L and S from the quantum numbers of
the individual electrons, one can ask
for the electronic state of the molecule.
how
the angular
momentum
con
To combine the
tum
contributions,
is
what
y/l{l
known
convenient to introduce vectors and to deal with as the vector model of the atom. The vector model assigns
it is
an orbital angular
momentum
vector
1) (h/2w)
momentum
if
the
a vector
represents the
magnitude s/L(L
1) (h/2ir)
momentum
The
of the
atom when
by L. by the vector
combinations
draw the vector diagrams, such as if one returns to the early, and not really correct, idea that the quantum number L implies an angular momentum of L(h/2ic) rather than ^L{L + 1) (A/2ir) and I an angular
those which give
turns out to be
much
of h,
momentum
of l(h/2ir) rather than y/lQ, + 1) (h/2w). In this way one would draw vector diagrams such as those of Fig. 1011 to represent the various possible combinations of 1 to form the net vector L. Similarly, one describes the total angular momentum due to the
atom by a vector
S,
and
in
terms of the
angular
momentum
one has
The previous discussion has assumed that the orbital and spin quantum numbers, and the corresponding angular momentum contributions,
can be separately treated. In fact this is not so; although in some systems it turns out to be a satisfactory approximation. Since it is the
250
i 2ir
i
*
L2*A.
2ir
ft
i
2?r
JL 27T
'2~
D
FIG. lOll
PS
is
L=0=
The vector additions of the angular momentum vectors of two porbit elecan angular momentum vector for the atom.
momentum of the atom that is really quantized, the meanquantum number of the atom is that which determines this total amount. The quantum number / is used, and the value of the total angular momentum of the atom is given by s/J{J + 1) (h/2ir). Again the vector model of the atom introduces a vector J to represent this magnitude and the direction of the total angular momentum. It turns
total angular
ingful
by
vectorially
combining
FIG. 1012
can
L and
S.
This
is
illustrated in Fig.
1012.
In terms of
t
in
which the
and S vectors
be combined
= 3Ss= 2
15.*. , 2 27T
2JT
L=2,
L=2
1
L=2
,_3
= 1 fK
= 27
*'2
of a
= 1, L = 2
251
of
is
given correctly by
.
.
J = L
The
L, S,
S,L
+ Sl,L + S2,
,\L
S\
atom can now be described, in a manner by the values of the quantum numbers
and
J.
customary to indicate the values of these three angular momentum quantum numbers by a term symbol. To indicate that L has the value 0, 1, 2, one writes, as mentioned earlier, S, P, D,
It is
.
.
ways that the spin quantum number can be combined with the orbital angular momentum quantum number is often an
Since the
of
number
important feature (energy levels with a given value of L are sometimes split into sublevels, depending on the coupling between L and S), we
indicate this
number
for L.
of
ways (2S
1)
is
<Sj,
an atom.
diatomic molecules are
of
We
similar, in
many
respects, to those of
an
Experimental, as well as theoretical, results for such atoms indicate that the atomic orbitals must orient themselves so that the
electric field.
component
of the angular
momentum
field.
of the
momentum
field will
be
M (h/2*),
where
M = J, J 
1,
0,
J
Again the vector model is convenient in that it suggests that the angular momentum vector J can take up various orientations relative to the
angular
applied field and that these orientations are such that the component momentum along the field is an integral, or half integral if J is
This is illustrated in Fig. 1013. a position to proceed to a similar description of possible electronic states of molecules and then to assign these states to the observed electronic transitions.
We
are
now
in
Molecules
it is generally impossible to calculate the energies and detailed electronic arrangements for the possible elec
As
for polyelectronic
atoms
252
Again
it is
by means
of values of the
quantum numbers
momenta, whose quantization can be immediately recognized. Just as for the case of atoms, this can best be done by first considering the allowed individual electron orbits and then investigating
principally angular
when
by
electrons.
The electron orbits of diatomic molecules are best described in terms of the orbits to which they would go in the limits of the united atom, i.e., the internuclear distance diminished to zero, and the separated
atoms,
i.e.,
Let us
the internuclear distance increased to infinity. first consider the united atom of some diatomic molecule
and investigate how the electron orbits are to be described as the nucleus of the united atom is imagined to be subdivided and the separate nuclei
that correspond to those of the diatomic molecule are formed.
initial effect
The
on the atomic orbits can be understood on the basis of the fact that the divided nucleus presents a field of axial rather than spherical symmetry. The effect on the orbits is comparable to that of an external electric field applied along the direction in which the bond is being formed. It becomes necessary, therefore, if the orbits of such a deformed atom
are to be described, to specify, not only the orbital angular
momentum,
axis.
Thus,
although an orbit of the united atom is characterized by its total angular n momentum, as indicated by the quantum number I = 0, 1, 2,
.
FIG. 1013
to
Vector diagrams
field
illustrating that
an applied
by
the angular
relative
1
state.
On
shown.
On
the
diagram, with
1)(h/27r) vectors,
is
given.
Either
diagram shows
that the J
M =1 2ir
=
1
<
M=0
M = l 2ir
.
27T
253
or
by the
letters s,p,d,
as the
molecule, these orbits will be characterized also (and for large distortions
better)
axis.
by the component
of the angular
momentum
For a given value of I of the initial atomic orbit, the quantized momentum components along the bond direction can have the The symbol X is usually used to quantum numbers 0, 1, 2, I. designate the quantum number for the component along the interhuclear are usually indicated by saying axis, and values of X = 0, 1, 2, orbit. (The nomenclature principle that the orbit is a a, ir, 8,
angular
. . .
is followed consists of using Greek letters for molecular quantities and Roman letters for atomic properties. Thus, in the spherical field of an atom, the orbital angular momentum quantum number is of major importance and is designated for each electron by I. For the cyclindrical
that
field of
momentum
quantum
feature
number
initial
for this
therefore, designated
by
X.)
With
step in the formation of a diatomic molecule from the united atom can be illustrated as in Fig. 1014. It is well to note the geometric
momentum
contributions.
by the imposition of an axial direction. The when the separated atoms are different, i.e.,
is
heteronuclear,
is
customary to represent the unitedatom limit at the left of the page and the separatedatom limit at the right of the page. This order is maintained in the diagrams for initial effects in Figs. 1014 and 1015.) A second atom affects the orbitals of a given atom by imposing a direction in space.
The three p orbitals, for example, which might be labeled p x pS) and pz are identical in the spherical symmetry of an isolated atom. When an axial direction is imposed, the orbit projecting along this direction, which has zero angular momentum in this direction and is therefore labeled as <rp, is differently affected than
being formed.
, ,
the two orbitals that project perpendicularly from the axis, have one
unit of angular
orbitals.
momentum
along this
axis,
irp
FIG. 1014
The
splittings
initial
step
in
are shown.
3dS
3d
3/J7T
3p
2pir
JF""
2p2p<r
2sa
UUnited atom
lsu
United atom "deformed" nucleus
with
Angular parts
of orbitals
254
IB
isg
"I
Hi
? 111
b *
N
6
o
a a o
fcfcfci
5
2 I
JE
o
o
.E
~^"^
"^h"^"'
O" o Ik CO
256
must be recognized
in order to see
how
from studies of the Heitler London description of is evident from the simple onedimensional illustration of Fig. 1016, two like wave functions can be combined either symmetrically, designated by g, or antisymmetrically, designated by u. These symbols must be attached to the description of the orbitals, as is done in Fig. 10156, when molecular orbitals are formed from like atoms.
familiar
As should be
the
molecule, or as
The
FIG. 1016
states
deduced
for the
wave
functions resulting
wave
node goes
is
node goes
to lower energy.
Infinite
separation
Slight interaction
bond formation)
257
now be connected
The two
limits
can be correlated with each other, to give a correlation diagram, when it is realized that the quantum number X is a good one even when the
axial field is very important as it is at intermediate internuclear distances. Thus, one joins up, as in Figs. 1017 and 1018, states with the same values of X, i.e., a a with a a state, a jt with a w state, and so forth. Fur
it is necessary to preserve the g and u character of the orbital. This can be done by joining orbitals designated by u for separated atoms with, for example, <rp states which, as shown by the wavefunction sketches in Fig. 1014, have the correct antisymmetry character. The correlation diagrams of Figs. 1017 and 1018 allow the electron orbits of a diatomic molecule to be described and the order of their
FIG.
1017
correlation
orbitals
lines indicate
the approximate positions which give the correct ordering of the energies of the molecular
orbitals for the indicated molecules.
SEPARATED
ATOMS
258
INTRODUCTION TO MOIECULAR'SPECTROSCOPY
and provide
essentially the
They are, therefore, equivalent to same basis for describing the elecdoes the use of the hydrogenlike wave func
with which the general shapes and energies of electron orbits of atoms can be described and the great difficulty of doing the same for molecules.
some information on the Something of the shape of the corresponding orbitals can also be deduced by looking at the shapes This is illustrated for the case of ap of the limiting atomic orbitals. 1019. in Fig. One should notice that two arrangements irp orbitals and that overlap, when the molecule is formed, are always the orbitals two of that to form a high electron density between one overlaps possible. The
correlation diagram gives immediately
relative energies of molecular orbitals.
The
the nuclei
is
of lower
energy
FIG. 1018
correlation
orbitals of
UNITED
ATOMS
25?
FIG. 1019 Diagrams indicating something of the shape of some molecular orbitals. These shapes indicated far up, a*p, xp, and w*p apply, for example, to the energy levels
in Fig.
cr2p,
7r u 2p,
and
jr2p in
Fig. 1018,
wave functions according to the number of nodes) and is said to be a bonding orbital. The second arrangement, in which the function must change sign and have a node between the nuclei, is of higher energy and is known as an antibonding orbital. In a similar way, one can draw the bonding and antibonding orbitals that are formed from the coming
together of other atomic orbitals.
orbitals
of electron
are
often used,
particularly
are
Exercise 103.
and
aid of Fig. 1017, suggest an electronic conground state of the molecule NO. (Note that each w energy level can accommodate a total of four electrons.)
With the
260
Exercise 104.
With the
an electronic con
Diatomic Molecules
The arrangement
tions that are based
by the individual electron descripon the correlation diagram. Some examples are shown in Table 103. If the molecule is composed of like atoms, the separated atom designation for the orbitals is more revealing and is used. For heteronuclear molecules, the united atom designation is used. As for atoms, the electronic state of the molecule depends on the
state of a molecule can be described
net or total electronic arrangement. Various electronic states can arise from a given electronic configuration, i.e., from a given description of the electrons considered one at a time. The electronic arrangement of the molecule as a whole can best be characterized by the net orbital angular momentum component along the internuclear axis and the net electronic spin angular momentum along this axis. The orbital component along the molecular axis, designated by A since this quantity depends on the individual electron contributions designated by X, is easily obtained by summing up the contributions of the separate atoms, for a, 1 for w, 2 for S, and so forth. The value of A = 0, 1, 2, is indicated by writing a term symbol 2, II, A, The spin angular momentum along the axis is, as for the atomic case, indicated by a superscript giving the
. . . . . .
multiplicity of the
state.
If
the molecule
is
is
symmetry,
i.e.,
the g or u property,
even and
is
labeled with a g
if
odd
the
number
u electrons
odd.)
Finally,
TABLE 103 Some Examples of the Descriptions Used for Electronic States (K is used to denote 2 electrons in Is orbits, L to denote 8 electrons in the 2s and 2p orbits)
Molecule
Ground configuration
(<rl) 2
H N
12+
l
(<r
Li 2
2
KK(<r,2s)'
KK
^t XK(
12+
2
K
n
c ls)als
^J, 3 2J
'2tf,
KK{<r g 2s)<r2s
ffl
3S
,2s) ! (<r2*)(T2p)*
"n,, 'n
(<r,2p)hr a 2p
LiH
iC(2ff) 8
K(2s<r)2p<r
i2+,
4
2+
2
CH
K(2sv)*2p<r(2pw)'
2~, 2 A, 2 2+,
S
261
a molecule < or
is
in a
two w
or 5
angular
momentum vectors,
<
>
>.
It
In view of
arise
is illustrated,
along with
We are now at a stage where we can describe, in terms of angular momenta, the different electronic states that can be expected for a given molecule, and with the aid of the correlation diagrams, we can tell, although only approximately, the order of these states on an energy
scale.
106. Potentialenergy
Diatomic Molecules
of states arising
from
different electronic
by the lengthy
It
and
labeled.
can
now be
When
this
can be done,
The way
here.
in
which electronic states are assigned to the transition band cannot be treated
is
The
subject
the principal basis for the assignment stems from a comparison of the
strongly affected
The nature of the rotational transiby the coupling between the electronic angular
one observes such features as
momenta
and the rotational angular momentum P and R branches with or without a Q branch, P and R branches with each line
of the states involved of the molecule.
As a
result
262
FIG. 1020
The potentialenergy curves for various electronic states of the molecule Cj.
Inc.,
(From
G
is
is
necessary.)
.
.
The
8,
symbol X
C,
is
a, b, c,
and A,
...
added
same
multiplicity.
80,000
10
C( D)
60,000
+ C('S)
C( P)
+ C( \SJ + cr 'a)
cr'oj
(cm
40,000
C( P)
+ C( D)
(e.v.)
C( P)
C( P)
20,000
0K10~ cm)
263
two or three
lines,
missing early
members
of the P, Q,
and
For some diatomic molecules, a fairly complete analysis of the ground and lower excited states can be made. For many more molecules, only
specific
electronic states.
Much
bonding
is
summarized
results
(1961)].
Appendix of ref. 2. A summary of some more recent has been given by P. G. Wilkinson [J. Molecular Spectroscopy, 6 :
in the
PRINCIPAL REFERENCES
1.
New
2.
York, 1944.
3.
Gaydon, A. G. "Dissociation Energies and Spectra of Diatomic Molecules," Dover Publications, New York, 1950.
:
4.
Mulliken, R. S.: Rev. Mod. Phys., 2(60): 506 (1930); 3: 90 (1931); 4: 3 (1932).
11
ELECTRONIC SPECTRA
OF POLYATOMIC MOLECULES
The wealth
of
in sharp
of the mole
bound highenergy
diatomic molecules.
The only
that are normally observed are, therefore, those from the ground to an
show up
in absorption spectra.
Only a
few bands arising from such transitions are usually obtained, and since
the samples under study are often solutions or solids, the absorption
bands are often broad and relatively structureless. (Spectra of compounds that will be studied later in this chapter are shown in Figs. 112, 1110, and 1118.) The revealing rotational structure of diatomic absorption bands is, therefore, absent, and a band does not immediately
reveal the nature of the electronic states involved in the transition.
difficulty
much work
has been
and
is
than the ground state of the molecule provide important testing data for theories of chemical bondThe geometry of molecules in excited states is not necessarily the ing.
of electronic configurations of states other
264
265
same
and ethylene
are, for
example, nonplanar in one or more of their excited states. In studies of reaction mechanisms, particularly those resulting from photochemical
excitation, such information
is
basic to a
detailed understanding of the mechanism. It should also be mentioned that the absorption bands due to electronic transitions, which usually occur in the ultraviolet or visible
spectral regions,
have long played an important role in the analysis and A number characterization of both organic and inorganic compounds. been developed which predict generalizations have of important empirical and intensity of the on the frequency effect structural changes the of absorption bands of a parent molecule. The relation between the electronic structure of the absorbing molecule and its absorption spectrum that will be introduced in this chapter provides some basis for the understanding of such empirical relations and for the use of ultraviolet and
visible spectra as a tool for the
The material
The
first
Most studied
of such systems,
and suitable
to illustrate
group
C=0.
The
is
similar
loss of the
axis along
which angular
momentum would
the largest and most studied group in this category, and after a brief
discussion of linear conjugated systems, the
way
in
The next topic deals with the absorption spectra produced by systems that contain a transition metal ion in a coordination compound. Many such systems are colored; i.e., they have electronic transitions that result in absorption in the visible region. The spectrum of such a compound is, therefore, an often referred to characteristic of the material. Analyses of such absorption bands in terms of the electronic states
266
state will
by which a molecule or an ion in an excited and return to its ground be investigated, and some features of the processes of fluores
OR GROUPS
11
Groups
Chemists have devised a number of ways for describing the ground One of these, due to G. N. Lewis, uses dot diagrams to indicate the number of bonding and nonbonding electrons in a molecule. Thus, for formaldehyde, HjCO, this approach would give a diagrammatic description of the giound electronic state as
electronic state of a molecule.
H
H:C::0:
where the placement of the dots represents the role of the outer electrons With the advent of quantummechanical descriptions based on the Schrddinger equation solutions for the hydrogenatom
in the molecule.
problem, these diagrams could be refined to show in somewhat more arrangement of the electrons. Thus, the diagrams of the type used in the previous chapter, i.e.,
detail the spatial
could be drawn.
These atomic orbital type diagrams suggest a method for describing the available electron orbits in molecules of this type. In view of the notation used for diatomic molecules, bonding p, or s and p hybrid,
orbitals projecting in the direction of the
orbital resulting
known
as a
a
bond.
There
267
the correlation diagrams of Figs. 1017, 1018, and 1019, a corresponding higher energy antibonding a orbital, not occupied in the ground state,
<r
atomic
orbitals.
This antibonding
usually denoted
is,
and <r*
orbitals
as
by a shown in
*.
atomic p orbitals that project perpendicularly from the bond direction and form a bond are said to be it orbitals. The overlap of such atomic orbitals leads to a bonding w orbital, which will be occupied in the ground state of H 2 CO, and a higher energy antibonding orbital designated by ir*. The
remaining electrons that are of interest in the study of electronic transitions of such groups are "lonepair" or "nonbonding" electrons on the
oxygen atom. They can, if hybridization of the atomic orbitals on oxygen is not considered, be located in the available oxygenatom orbitals, which are a lowlying 2s orbital and the remaining 2p orbital. If only
the higherenergy 2p orbital
transitions,
it
is considered to be involved in the observed can be designated simply as a nonbonding orbital and the
for
it.
momentum
We
will see,
can be drawn well enough so that the symmetry of the orbitals can be deduced, and the behavior under the symmetry operations of the molecule
will
molecules.
bond that
an
be
H CO
2
will
(<r
CH )
(<r C H')
(rco)
2
]
(ttco)
(o)
The three <r bonds to the carbon atom are thought of as being formed from sp 2 trigonal hybrid orbitals on the carbon atom. The ir bond between the carbon and oxygen atoms then is formed from the remaining carbon atom p orbital and one of the oxygen p orbitals. The brackets enclose the lowlying inner and bonding electron orbitals that are not
normally expected to be involved in the transitions studied.
It is
enough,
2fi 8
2 )
some
by
Some
spectroseopically
important orbitals of
H2CO and
their
symmetry
properties.
269
and so forth. In the above, as is customary, a superscript 1 is understood and is not written when an orbital is singly occupied. Expressions such as those given above constitute electronic configurations for the various electronic states of the
H CO
2
molecule considered
here.
Exercise 111.
CH CN molecule.
3
of a molecule is adequately
One can, however, recognize that the total electronic wave function must have a symmetry that is. compatible with the symmetry of the molecular skeleton. It is this symmetry behavior that best characterizes electronic states of polyatomic
along an axis.
molecules.
First one
orbitals.
momentum
effectively
H 2 CO, or any symmetric ketone, belongs to the point group C 2 . The character table for this group is shown in Table 111. Assignment of the orbitals of Fig. 111 to symmetry species can readily be made by investigating whether the orbital is left unchanged or changes sign as a In this way the result of the four symmetry operations of the group. symmetry classification of the individual orbitals, shown in Fig. 111, is
obtained.
It is
must consider the symmetry types of the The molecule being used as an illustration here,
individual
now
wave function
of the
TABLE 111
CgB
The
C
c2
Character Table
E
1
<r v
Ai
1 1
T.
A
B
1 1 1
1
1
Bi
2
1 1
1 1
1
Tx
Ty
1
270
TABLE
12
<p(1).
Presumed
to
Be of the Type
A it
and
<p(2),
C,
+i.(D
1*>(1)
+ M2)
(+1)( + 1MD>(2)
(
1(2)
+ 1)(1)(1M2)
= 1>(1M2)
+ 1.(1)*>(2)
1.(2)
(DC1M1M2)
=
+ M1),(2)
mation
sufficient for
symmetry
* = #>(1M2)*(3)
where
>(2)
<p(l) is
the
wave function
results of
The
are
known. Thus, for example, if electron 1 is in an orbital of type A 2 and electron 2 is in an orbital of type B h the result of symmetry operations on <p(l) and <p(2) could be tabulated as shown in Table 112.
The
effect of the
symmetry operations on the product ^(1)^(2) is We have used again, as we did in the symmetry behavior of the transitionmoment inteis equal to
The product
With
<p(l)(p(2) is
2.
can calculate
simplified
one
total electronic
wave function
is
of the molecule
The task
greatly
when
many
(in
all) of the orbitals are occupied by two electrons and (2) that the product of one nondegenerate representation and itself necessarily leads to the totally symmetric representation. In view of this, the net char
usually
acter for
all
is
displayed, can then be easily deduced from the symmetries of the singly
occupied orbitals.
The
results are
shown
in
Table
113.
271
Electronic States of
TABLE 113
Some
Electronic Configurations
and
Formaldehyde
Configuration
Symmetry
of elec
Transition
moments from
tronic state
ground state
[Inner electrons] (x) 2 (n) 2 [Inner electrons] (ir)*(n)(?r*) [Inner electrons] (ir)(n)*(ir*) [Inner electrons]
(ir)
2
A,
A B
A,
2
W= =
kl kl =
\fy\
(n)(<r*)
= M=
*.
ImI
0;
,
/i,
0;
^ *
Exercise 112.
Verify the
in
Table 113
One further feature of the electronic states of molecules must be The description has, so far, ignored the relative directions of spin of the electrons. The Pauli principle requires that the spins of two electrons occupying the same orbital be opposed but allows, when orbitals are occupied by single electrons, either spin orientation. It follows that the ground state of H 2 CO must be a singlet state, i.e., the net spin must equal zero, since all the electrons are paired and each pair must have opposite spins. For the excited states considered above, howmentioned.
ever, the net spin can be either zero,
state, or unity,
i.e.,
i.e.,
The
designa
molecular state.
It can be mentioned in this connection that the rule based on atomic spectral results, and known as Hund's rule, is also
if
both singlet
and
have a lower energy than the corresponding singlet Thus, lower energy electronic states are to be expected when the
above excited configurations are occupied by electrons with parallel spins than when they are occupied with paired spins. This qualitative
discussion
is
as far as
we need go
must
which we
will
be concerned.
Now we
see
if
A schematic absorption spectra of a carbonyl compound such as formaldehyde or methyl ethyl ketone,
this section is to see
if
is
shown
in Fig. 1112.
The
object of
272
If
of the
The
compound that
ground state and each of these excited states can be expected to be induced by electromagnetic radiation. According to the discussion of Sec. 40 it is necessary for one of the integrals
transitions between the
= Kl =
Mx
or
M*
MsTcitodM^ground *"
Knowledge
of the
compound.
a
S
a
E
1 1
1,500
2,000
2,500
3,000
3,500
4,000
in
273
symmetry
of the
wave functions
be nonzero.
is sufficient
the integrals
may
(One can, in
get
fact, use
approximate wave
some
whether
how
The integrals, like all observable properties, must not be changed be.) by the symmetry operations which take the molecule from one orientaThus, unless the symmetry species tion to an indistinguishable one. to which ^WitedMi^ground belongs is A h the value of the integral must be zero. Similar statements can be made for the transitionmoment integral in the y and z directions. The ground state for the molecules considered here, and for all molecules with no unpaired electrons, has the symmetry type ili. It follows that the entire integrand has the symmetry Ai if Excited and x lilted and y, or ^ eicited and ju s belong to the same symmetry
ii
,
type.
Thus, just as in vibrational transitions, an electronic transition from a totally symmetric ground state is allowed if the excited state
y. x ,
n y or
,
\i z ,
i.e.,
Tx Ty
,
or
z.
an analysis applied to CH 2 are shown in Table 113. The selection rule prohibiting changes in spin that is operative in small atoms and diatomic molecules appears to be fairly well obeyed in
The
results of such
simple polyatomic molecules. Again, however, the presence of a nucleus with a large nuclear charge results in a strong coupling of the spinning
electron with the orbital motion of the electron
relative
Even
While
i.e.,
unimportant in absorpwill
role in fluorescence
and
phosphorescence.
on the basis
tion bands.
comparison of the observed band intensities with those expected of the transitionmoment integrals provides the most frequently used approach to the assignment of electronic states to absorp
As mentioned in Sec. 49, a completely allowed transition, such as that from the ground state to the A x excited state of formaldehyde, is expected to have an intensity fa(v) dv which corresponds to an
oscillator strength, or / value, near unity. On the other hand, transitions that are predicted to be forbidden on the basis of the symmetry treat
ment
illustrated above can occur to such an extent that weak absorption bands are observed. The / values for such bands will be much less than unity. One mechanism that allows forbidden transitions to occur
274
symmetry as does the molecule in its equiAs a result, the skeletal symmetry to which the electronic wave functions must conform is, for the H 2 CO example, not strictly C 2 , and the prohibitions based on that symmetry group are not strictly adhered to. The generally accepted assignment for the observed carbonyl bands is shown in Table 114. Two other general methods for aiding in the assignment of absorption bands are used. The first of these is concerned with the direction of the transition moment, i.e., the polarization of the absorption. The
that do not have the same
librium configuration.
analyses given in Table 113 indicate that a determination of the direction
of polarization
can be used to determine the direction of the transition moment. In some cases, a suitable crystalline form can be found that permits such
studies.
Another assignment aid comes from the shift in the wavelength of the ab.orption band that accompanies solvation of the molecule. It is found, for example, principally on the basis of empirical correlations,
that absorptions due to
n > t*
ir
>
transitions are shifted to shorter wavex* transitions are shifted to longer wave
molecule
is
increased.
This correlation
theoretical basis.
[Cf.
TABLE 114
Assignments
Number
of
Compounds)
Assignment
"band max
/
(osc. strength)
(A)
Configuration
change
1,700 1,800 2,800 3,500
7T
IT*
M,
Bi
Allowed
re> a* re x* re  i*
'A,
A,(?)
275
would lower their energy and lead to a greater energy change, or a shorter wavelength band, for a transition that promotes one of these electrons.
An
interesting
the process by
which molecules
energy and
This process, as we
will see,
can
becoming standard, when transitions between two electronic states are considered, always to write the higherenergy state first. Thus, for example, the band in the H 2 CO absorption spectrum at about 1,800 A would be referred to as due to a B X < *Ai transition. If the same transition were studied in emission, one would write 'Bi A x When, as is
1 l
.
much
However, when the transition is discussed in terms of the configuration change of an electron of the molecule, the relative energies
can
arise.
two configurations are usually evident, and one writes the initial electron orbit first and then an arrow pointing to the new orbit reached by the electron.)
of the
1 1 3. Draw the tt and it* orbitals of ethylene, and assign them symmetry types in the point group to which ethylene belongs. To what symmetry types do the ground and first excited (ir)(jr*) states belong? Would a transition between these states be allowed, and, if so, in what direction would it be polarized?
Exercise
to
AND
AROMATIC SYSTEMS
In molecules containing conjugated double bonds and in aromatic it is now clear that the k electrons, i.e., those in the 2p orbitals
systems
that project perpendicularly from the plane of the trigonal sp 2 orbitals forming a bonds, are responsible for the absorption found in the nearultraviolet or even the visible region. In studying such systems we can, therefore, concern ourselves with the possible orbitals that can arise from the atomic 2pw orbitals. A very simple but surprisingly successful
approach,
known
276
conjugated systems.
it
leads
In the following to are spread out over the entire molecular skeleton. and molecular considered, orbitals will will be systems section, aromatic be set up for benzene by means of the classical molecular orbital approach which combines the 2px atomic orbitals into appropriate molecular
orbitals.
113.
at longer
known that conjugated systems have absorption bands and longer wavelengths as the number of conjugated double bonds gets greater and greater. In fact, long conjugated systems are These often colored, i.e., the absorption band is in the visible region. general features, as well as the wavelength and intensity of the absorption
It is well
band for a given molecule, can be understood on the model for the x electrons of the molecule.
basis of
a very simple
The structure, as indicated in Fig. 1 13, consists of a planar nuclear array. The carbon atoms can be considered to form a bonds with sp 1 trigonal A total of eight orbitals and x bonds with the remaining p orbitals. electrons will occupy the x orbital system. A treatment of the x electrons can be based on the idea, long held by
chemists, that these electrons are delocalized and are not confined to a
throughout which, subject to the wave functions that can be calculated from the Schrodinger equation, the electrons are free to move.
Outside the molecule the potential energy, on the simplest model,
is
FIG. 113
<r
bands, Indicated by
The bonding and structure of octatetraene. Each carbon atom forms three Each remaining 2p orbital, shown os with fp' hybrid orbitals.
an atomic
trie
delocalized
bonding.
ELECTRONIC SPECTRA
OF POLYATOMIC MOLECULES
277
assumed to be
infinitely high.
is
shown
in Fig. 114.
set.
not unambiguously
move about
is
half a
One bond
appropriate rather
and ignoring repulsion between the ?r electrons, one can deduce the allowed orbitals and their energies. The quantum mechanical problem has already been solved in Sec. 15. There it was found that the wave functions for the particleinabox
problem are
I = A
sin
n =
1, 2, 3,
(2)
"
8ma*
(3)
The Pauli exclusion stipulation that no two electrons can have the same quantum numbers requires that no more than two electrons, one with spin +i and one with spin ^, be assigned to a wave function with a
FIG. 114
tali
by
to
the
The
Hie
that
leads
278
given value of
The occupation
of the available
it
molecular orbitals
that which
The
is
expected
is
arrow in Fig.
orbital as indicated
by the by
46
.4>)
^
would cause
(4)
The frequency
with a
v
of radiation that
=
=
9.5 A, to be
27,000
cm
(5)
is
to be
maximum found
at 33,100
cm
1
.
The agreement
is
surprisingly good.
that, as discussed in
is
calculated.
The
32iVe
!!
aV
10 19 sec 1
3ir/icl,000
1.9
cm 1 mole"
liter
(6)
1.1
10 19 sec 1
cm mole"
1
liter
(7)
is
satisfactory.
number
method
The
chief
enced by the
ir
electrons,
is,
however,
its simplicity.
Exercise 114. Note the similarity between the orbitals of Exercise 111 and the n = 1 and n = 2 particleinabox wave functions that would be drawn for the ground and first excited orbitals for ethylene using the
particleinabox model.
Exercise 115. What are the calculated and observed / values for the longest wavelength irelectron transition of octatetraene? Exercise 116. Lycopene is a linearly conjugated hydrocarbon conIt is responsible sisting of all double bonds alternating with single bonds.
for the red color of tomatoes.
279
* v* transition and compare with the observed band which occurs at X = 4,700 A.
the w
114. Electronic States
maximum
and Transitions
in
Aromatic Systems
description of the ground electronic state of aromatic goal that occupied the attention of many early organic was systems a Following the advent of quantum organic chemists. physical and
An adequate
states,
A number
of approaches to the description of the excited 7relectron states of aromatic systems have been used. An introduction to the electronic spectra of aromatic systems can, perhaps, best be given in
terms of a simple
classification
orbitals, applied to
The importance
of the
symmetry
of the molecular orbitals and the electronic states will be brought out,
and
it
will
The treatment
can be extended to other aromatic systems, but this will not be done here. As in the previous section, attention will be centered on the 2prr
orbitals,
shown
for
benzene
in Fig. 115.
It is first
necessary to see
how
The guiding
principle here
is
must conform to the That is, by an argument analogous to that used in discussing the symmetry of normal coordinates in Sec. 64 and illustrated for locabzed orbitals in Sec. 111, each molecular orbital must transform, under the various symmetry operations, according to one
or molecular orbital, of the benzene molecule
symmetry
of the molecule.
Let us
now
see
if
such
by
atomic orbitals.
FIG. 115
280
Character Table
D,
A,
E
I I
2C e
2C1
3C
3c;
I 1
A,
B,
1
I
1 X
1
1
1
B2
Bi E,
2 2
1 1 2
2
i i
i
T,
1
T*,T y
The
is D The treatment can be somewhat simplified if the symmetry about the plane of the molecule is, for the time being, ignored. It is enough to treat the wave function above the horizontal plane of the molecule or below that plane. Later the fact that all px orbitals are antisymmetric with respect to this plane can be added in. With this
cule belongs
problem can be analyzed in terms of the simpler which the character table is given in Table 115 and the symmetry elements are illustrated in Fig. 116.
simplification, the
point group
8,
for
The
six
2px atomic
i.e.,
orbitals
form a basis
are
and
FIG.
1 1
6
Da
point group.
Note
ease for
the Dbi point group, symmetry with regard to the plane of the molecule
Cfin
not considered.
C gT Cj
281
as
p' /l
p"
=(010000
0^
character for
E =
^000100^
10
character for
and
so forth.
In this
way one
tl
2C6
2C 6
C7 6
0C2
0C2
As
it.
in the
this representation
can be
Ah B E
x,
x,
and
E
l
2 , i.e.,
= A
+B +E +E
l
(8)
We
type
Ei,
see
from
1,
one according to
Bh
and another pair according to E 2 We must now see what combinations of the atomic orbitals have these transformation properties.
is
Rather than develop this, we will present the results and merely check that they have the correct transformation properties. (The two nondegenerate orbitals can, in fact, be constructed
the suitable combinations.
by
inspection.)
The molecular
orbitals that
282
Electrons of
Benzene
Symmetry
type
Molecular orbital*
fa^
iAi>i
Al
Bi Ei El
*
= = <An = ^e, = H = ^e =
<ls
+ <Pb + <Pc + <Pd + <Pb + <Pf <Pa <Pb + <Pc .<Pd + <Pe <Pf 2^>x + <Pb <Pc 2<p D (ps + <Pf <PA + 2<PB + <PC f>D %PB <PF 2<PA <PB <PC + 2<fD <PE <PF + +<PD 2<PE + <pF <PA
<Pa
2(fiB
<fiC
Lowercase letters are used as subscripts to identify the molecular orbitals, just as lowercase letters were used for individual electron orbitals in atoms and diatomic Capital letters are reserved for the symmetry type and the net electronic molecules.
state of
an atom or molecule.
and it may be more revealing to consider the sum and the difference of the two functions given in Table 116.) The form of the molecular orbitals can be seen by drawing the wave One should recognize that a corresponding functions as in Fig. 117. function, but with opposite signs, will project out on the other side of the benzene ring. Also one should keep in mind that each molecular orbital can accommodate two electrons.
in various ways,
The order
the higher
is its
energy.
a,i
are in a
wave
function,
of Fig. 117
lowest energy and the &i function at the top has the highest energy.
shown
in Fig.
118.
These which
to evaluate.
The symmetry
are also
shown in Figs. 117 and 118. The fact that the pr wave functions, or any linear combination of them, have opposite signs on
opposite sides of the plane of the molecule allows, after inspection of the wavefunction diagrams of Fig. 117, these designations to be given to the
orbitals previously labeled a\,
ei,
e 2,
and
&i in
group.
Exercise 117.
117, verify the
classified
By
inspection of the molecular orbital diagrams of Fig. classifications of a lg , e lg , e iu , and b ig for the orbitals
on the basis of
symmetry
as
oi, ex, e 2 ,
and
fei,
respectively.
bi(bi)
ei(e iu )
Cl("l B J
a, <ai)
Dark gray Schematic representation of the molecular orbitols for bemene. symmetry type is [The parts. negative outlines gray light of outlines positive parts $;
FIG. 117
given
in
terms of
and,
in
parentheses. Da)
FIG. 118
The relative energies of the individual Symmetry designaon the basis of the
De
the.
point
group
283
and,
in
D$s group.
284
Now it is necessary to consider the assignment of the six 2prr electrons to the available orbitals in ways that correspond to the states, ground and excited, that are involved in spectroscopic transitions. It
will
resulting
electrons.
The electronic configurations that need to be considered (remembering that two electrons can occupy a given orbital and four a doubledegenerate orbital) are that of the ground state and that of the excited
states
which result when one electron These are indicated in Fig. 119.
is
promoted to an
e 2 orbital.
The symmetries of the electronic states of these configurations can be derived from the products of the characters for the symmetry species of the orbitals occupied by each electron as described for localized groups in Sec. 111. Thus, since the ground state involves pairs of electrons occupying the same orbitals, the total symmetry of this electronic state
must be A lg The symmetries of the excited states can be obtained by analyzing the direct product of the representations of the orbitals e lg and e 2u occupied by the lone electrons. The direct product of the char.
acters of the Ei s
and
2C
E iu
representations
is
2C\
3C 2
3C' 3
oh
3<r
3<r d
2S e
2S 3
XJS la
XB.
1
4
01
situation encountered with nondegenerate representaa reducible representation is obtained. It is necessary to analyze
TABL Ell7
D,i
Alg
E 2C
1 1
2C\
CI
3C 2
3C 2
(Th
&T V
3tTd
2S e
2 3
A iu
At, Aiu Bi Biu
1 1 1
1
1 1
1 1
_1
_1
_J
1
1 1
Bt a
Bi
1 1 1 1 1 1
1
Ela E lu
Eig Eju
2 2 2
2
1 1 1 1 2
1 I
_1
I
_1
J
I
I
J
i
i
T,
i i
_1
1
2
2 2
_1 _1
1
2
2
2 2
1
i i
2
2
T T
2
2
285
terms of its component irreducible representations in order to determine the symmetries of the states arising from singleelectron occupancy of the e ig and e 2 orbitals. This can be done by application
this in of
8,
and the
result
is
checked, that
/CBtg
A.E 2t
Xb,
xs*.
+ Xtf
two
(9)
The
states
with symmetries
Bm
and
B iu
and
sym
metry E\u
To a
first
states,
occupancy of the same set of individual orbitals, correspond to the same It is a matter of considerable difficulty to total electronic energy.
deduce, in a purely theoretical way, the relative energies of these states and the ground state. Furthermore, two electrons in each of these
excited states need not have their spins paired.
to have both singlet
It is possible, therefore,
and
triplet states,
and
as suggested
by Hund's
lie
rule
lower
than the corresponding singlet states. Many attempts have been made to calculate the energy pattern for the excited states of the benzene
FIG. 119
Distribution of the
7r
electrons of
benzene
in
the ground
and
first
excited elec
tron configurations.
P*5*=
Groundstate
configuration
Excitedstate
configuration
286
One must, therefore, make what deductions one can from the observed spectrum, shown in Fig. 1110, about the states involved in the various absorption bands.
It is first
and
belong to a symmetry type that contains Tx T or Tz One sees from y Table 117 that, for a D 6h molecule, transitions to the states with sym,
E lu
band
in the absorption
spectrum
of
of
1
E Xu
state.
assigned to the
E lu * A
1
lg
transition.
Some assignments of the remaining absorption bands can be made. The very short wavelength band, around 1,500 A, is attributed to a
FIG. 1110
K. S. Pitzer,
in
(From
"Quantum Chemistry,"
PrenticeHall, Inc.,
Englewood
Cliffs, N.J.,
1953.)
5r
\B ta
or
%,  'A,,
1
Rydberg series
31,500
2.000 X
in
2,500
3,000
3,500
287
in
increased, as in the
Rydberg
series usually
Such highenergy discussed in connection with the hydrogen atom. treatment given here. It has the in included transitions have not been
been suggested that the band near 2,100 A is due to either the transition lB^iiAig or 1 E ig <^ 1 A u These forbidden transitions could occur as a result of "borrowing" intensity from the nearby intense band at
.
1,800
A or
of appropriate symmetry.
1
The
This
is
B iu < A ig
1
transition, prohibited
from the
electronic states, can again be allowed as a result of coupling with a The very weak absorption at about vibration of 'suitable symmetry. forbidden transition *B u * l A it highly 3,300 A is attributed to the
i
.
It should
symmetry,
remains a task of
considerable difficulty definitely to identify each absorption band with a The assignments suggested here are transition to a particular state.
made
bands
of certain symmetries.
As
in
by orientedmolecule and the Some of the ways in which more complicated effect of substituents. aromatic systems can be approached have been discussed by R. N. Jones [J. Am. Chem. Soc., 67: 2127 (1945)].
ing groups, aids to the assignment are provided
Exercise
level
1 1
8.
On
draw an energydiagram showing, by means of horizontal lines, the energies of the various electronic states of the molecule. Attach electron volt and kcal per mole energy scales to the diagram. Exercise 1 1 9. Treat the molecule cyclobutadiene
of Fig. 1110 to electronic states of the benzene molecule,
\c /
c
II II
\c=c/ /
c=c
I I
/.
\H
\H
in a similar
manner
to that in
288
form, these molecular orbitals. (c) Arrange these orbitals in order of their energy. (d) Assign the * electrons to 'these orbitals in accordance with the lowest and the first excited electronic configurations. What are the symmetry species and multiplicities of the electronic states that arise from these configurations?
(e)
(a) Deduce the number of molecular orbitals of the various symJ metry types. (b) Draw, by inspecting the way in which the orbitals must
trans
What
transitions
would be allowed?
COMPOUNDS
The absorption spectra of compounds or ions containing transition metals have long been used to characterize these species empirically. Coordination compounds, in which a number
of electronrich groups, called ligands (such as
ion,
:
NH H
3,
CI
),
species.
comprise the most extensively studied type of transition metal In this class one has, for example, the familiar, colorful ions
gives an intense blue color,
all
bands in the visible, as these familiar examples do, or in the nearinfrared or nearultraviolet spectral regions.
In recent years an earlier theory developed by Bethe and by Van Vleck has been applied, and extended, to these systems, and it has
ime) 2 which forms a red crystal. Almost the transition metals have absorption
coordination
and Ni (dimethylglyoxcompounds of
become
compounds can be
part, in terms of transitions involving the electrons in the incomplete outer d shell of the metal ion. (Other absorptions, usually more intense and farther out in the ultraviolet, that occur are attributed to what are called chargetransfer transitions. In these transitions electrons are, to some extent, transferred from the ligands
most
to the metal or from the metal to the ligands. transitions will not be dealt with here.)
These chargetransfer
The treatment of the d orbitals that has been used and that allows the absorption spectrum of a coordination compound to be related to the properties of the metal ion and the ligands is known, in its simplest form, as the crystalfield theory and, when a more detailed treatment the
of
ELECTRONIC SPECTRA
OF POLYATOMIC MOLECULES
is
289
theory.
In
its
is
all
supposes that the ligands impose on the central metal ion an electric field whose symmetry depends on the number and arrangement of the ligands
and whose strength depends on the electrical nature of the ligands and, more particularly, on the repulsion which those electronrich groups (The coordination compound exert on the d electrons of the metal ion. by the attractive interaction primarily held together being pictured as is
of the charge of the
It will
such as exists in the free ion the i.e., they constitute a degenerate
five
set.
some
of the
To
we must
proceed, as in the benzene analysis of the previous section, to find orbitals that have symmetries compatible with that of the system, i.e., with the arrangement of the ligands. When this is .done, the relative energies
of these orbitals can be investigated
The procedure
of
is
such complexes
is
shown
group
in Fig.
1111.
Since
all
symmetry
is
of the point
group O*.
The
1 1
8
O h Character Tabl e
8C
o
Ai,
E
1
6C 2
1 1
6C 4
1
1
3c;
1
6S 4
1 1
8S e
3o*
6avj
A lu A ig
Azu
1 1
1
1 1 1
1
1
1 1
1 1
1 1
1
1
1 1
1
1
1 1
1
1
2
1
2
E,
2 2 3 3 3 3
Eu Tu
Ti u
1 1
i l
l 1
2
2
1
2
3
1
Tn
Tzu
1 1
1 1 1 1
2 1
1
1
1 1
J
3
3
1 1
1
X) 1 yi i z
1
1
3
1
290
symmetry elements
are
shown
in Fig.
1111.
Treatments similar to
that given here for octahedral complexes can, of course, also be given for
The
d orbitals of an
I
atom
2,
the magnetic
quantum number
can have the values 0, 1, 2. The five d orbital wave functions that (These, arise in this way were shown in terms of J = 2 in Table 51.
of course, define only the angular factors of the orbitals.
radial factor
also be introduced
wave function completely. For considerations of enough to concern ourselves with angular factors.) The dorbital functions of Table 51 are appropriate to a system with spherical symmetry. They provide, furthermore, basic functions from which orbitals can be constructed that have symmetries compatible with the octahedral arrangement of the ligands that are now imagined
symmetry,
it is
The procedure
in
is
similar to that in
is
done
five
will
be
d orbital
wave functions
FIG. 1 111 (a) The geometry of an octahedral complex. and the complex belongs to the symmetry point group symmetry elements of the Oj, point group.
All six
O;..
(b)
Some
representative
NH.
^
c 4 .c;
*T
NH.
(a)
to
Cj and C 4
ELECTRONIC SPECTRA
OF POLYATOMIC MOLECULES
291
can be recognized as containing the doubly degenerate irreA set ducible representation E g and the triply degenerate one 2V latter representathe according to transform of three orbital s that
group
tion can be
directly
These are indicated diagram matically, along with the d zv d a dg, notaDiagrams can be drawn to represent tion usually used, in Fig. 1112.
the two orbitals that transform according to the E g representation by drawing three pictures and imagining linear combinations of these to be
made
the
als,
so that
Eg
It is
of these
shown
and
dn.
unique and that the One must, however, keep in mind that no orbitals that project along orbitals with E g symmetry consist of a pair of lowercase symbols, the of use (To be consistent with the cartesian axis.
such as
s,
p, d,
orbits, the
symbols
tig
and and
<r,
jt,
3,
e g will
FIG. 1112
orbitals.
3
2.")
d <*i z>
d (2_ z Z)
292
T 2g and E g .)
We now
consider the
and
orbitals that
octahedral complex.
The energy
difference
d orbitals can, in a
it
might be mentioned, to the deduction that the energies of the molecular orbitals of benzene are arranged as in Fig. 118.) One supposed that
the six ligands occupy sites along the cartesian axes of Fig. 1112.
These
effect
along these
experience,
e g orbital will
more
fa g
orbital.
lie
Thus the
two
e g orbitals
can be expected,
t 2g
at
orbitals.
The
exact
amount
of splitting of the
It
cannot be
satisfactorily calculated.
of the interaction
metal ion and those of the ligands. The amount of splitting must be deduced empirically, and as we will see, Finally it should be spectroscopic studies often allow this to be done.
of the
mentioned that
it
or
lODq
sets.
and
is
t 2g
orbital
finds
A = 10 Dq
to be of the order
of 10,000
cm
1
,
increased to
FIG. 1113
field.
The extent of
A or
lODq.
here.
293
The quantity
A,
can be made between this quantity and chemical properties of both the transition metal ions and the ligands that have been studied.
of interesting correlations
number
We
splits
ion in an octahedral complex and have recognized that the ligand field
Now we
when the d
Coordination Compounds
d electron, such most easily treated. The effect of the crystal field on the states of such an ion will, therefore, be discussed first. In view of the survey of atomic, or ionic, electron states indicated
as Ti 3+
,
The
are
in Sec. 103,
i.e.,
state;
be 2
and thus 2S
+1 =
is
2.
For no crystal
2
state.
When
ligands are
now
accommodated,
a set of lowerenergy
Ug
orbitals
and a
set of higherenergy
The
electronic
(fo,)
1
two
and
(e,)
1
.
Since there
is
similarly described
T ig and
E.
One sometimes indicates the effect of the crystal field for this one d electron example by a diagram like that of Fig. 1114. In a sense, which will be more evident later, this is a correlation diagram between the
situation for the spherical field of the ion at the left and the strong crystal field at the right. Various ligands will have crystal fields of
various strengths and will correspond to positions along the abscissa. For example, the aquated Ti ! + ion [Ti(H 2 0) 6 ] s+ has an absorption band at 4,900 A, or 20,400 cm 1 which can be identified with the transition
,
This observation allows the vertical dashed line to be drawn in Fig. 1114 at a position where the splitting is 20,400 cm" 1 Alterna.
^ <
?V
294
tively
for
of the crystalfield
is
example since it has two outer d electrons and We wish to draw a diagram, like that of complexes. octahedral forms
The
the
cmsituation when
1
.
there are
two d
electrons.
any strength
of crystal
two I = 2 field be combined to 103, in Sec. discussed can, as electronic contributions and or states. Now, F, P, S D, or i.e., G, 0, give L values of 4, 3, 2, 1, these features were not mentioned in the earlier discussion, the assignment of the two electrons to the available d orbitals must be made in
can be picked
off.
An
illustration of
how
1 The energylevel diagram for a metal ion with one d electron, i.e., d conis energy scale effect. The figuration, showing the effect of increasing crystal field The posiarbitrarily assigned the value zero for the ground state of the undisturbed ion.
FIG. 1114
tion of [Ti(OHj) 6]
3+
is
A determined
1
[Ti<OH 2 ) 6
P
State
'E g
configuration (e)
State
'T^
1
configuration (t 2g )
5,000
10,000
15,000
20,000
25,000
A (cm
Zero
crystal field
Large
crystal field
295
L can
by G. Herzberg, "Atomic Spectra and Atomic Structure" (pp. 130135, Dover Publications, New York, 1944) and will not be repeated here. One finds by this means that the d 2 configuration can only lead to states P, F, S, D, or *G. The energy
3 Z 1 1
is
way
drawn
for the
V 3+ ion.
would be expected
for a d 2 ion subjected
Let us
now move
states that
field.
to a strong crystal
The three
(k g ) 1 (e g ) 1
and
(e)
2
.
respond to
Now, to find what electronic states these configurations corwe must, as in the previous treatments of localized groups
direct product of the representations
Analysis of the
(<2)
configura
Table
119.
In a similar
way the
two configurations can be found, and the results of these analyses are shown in Table 1110. Similarly, the electronic states that arise from other electronic configurations can be found from the appropriate direct products of irreducible representations, and these results for all nine configurations of an incomplete d shell subject to octahedral symmetry
TABLE 119
Illustration
Configuration (hg)*
Oh
Ct
C\
Se
XT,,
3 9
1 1
1
1
1
1
1
1
1
1
1 1
XB,
2
3 3
1 1
1 1
2
3 3
1
1
1
XT la
XT,,
1
1 1
1 1
1
1
XA U
XB,
XT,,
XT U
9
1 1 1
296
Free ion
symmetry
*
!
d>,
<.)
(*.)'
T 2
>,.
d\ d 8
(U*
d\d?
(e)
3
WW
()
2 ,
A,, 'Ai,,
T. 3 T 2o
ir.,
fol'fe)'.
(<i.)
s ,
2 2 r l0 2r l(
, ,
(.)
?,,
(*i)*
<A 2 ,
Ai,
3
*T i0 *A ln M,, 2T,,, , *T 1( T
,,
2T
d*,
(e) 4
(W() 3
(WW (WW
(W
d
TU
r,,
*,
Tip, >T 2I *E g , 3>T ig 2'T 2e 2iA,, 'A,,, 3' t T,,, 3T,,, 3 A l5 A 2o 23, 2r lln 2r 8 ' 'A,,, >A,, >,
>T,,
,
2T
s
1(
2T
r, ia,, j? >r 2
T
2
r 28
l0 ,
r,,
*T U *r lln
,
M, A 2o 2^ 2'7 M, 2^, *T lg *T lg
2
, ,
1( , )
2*T 2 2'A lg
*A 2 ,
VE
B,
4T,
IT,,,
4r,
2l,,
*A.
A 2o
2, 2 2 !T
2T 2o
110.
(We
and
it is
systems.)
Again,
when, as in the
(2)
and
(e)
configurations,
same
orbital description.
By
(e)
1
2
1
A ig Ai g and Eg and
each of the type
that the
(ti g )
(e g )
T ig and T 2g
fields,
is
deter
orbitals
and the
297
e orbitals. The righthand limit of Fig. 1115 can be drawn, with the states of the d* configuration, on this basis. For intermediate field strengths the tendency for the electrons to
occupy the lowenergy t ig orbitals as well as their tendency to avoid one another, which produces the different states of the free atom, are important. The energylevel pattern for such situations can be drawn
FIG. 1115
d2
ion.
On the
left is
the
The correlation
Free ion
Strong
crystal field
\3
'
298
by
joining
up the appropriate
in
and
1114.
The way
first
shown by
by means
of a grouptheoretical
derivation of the relation between the atomic states of the spherically symmetric problem and those states described by the crystalfield notation appropriate to the potential field of octahedral symmetry.
The
it is
momentum
of the
atomic state
correlation of atomic states and the octahedral crystalfield descriptions are determined by the atomicstate symbol, i.e., S, P, D, and so forth.
The appropriate
one must also preserve the spin, or multiplicity, of the electronic states. When this is done, the correlation lines shown in Fig. 1114 can be
drawn.
It
is
now
an atom with two d electrons, i.e., a d system, is in many respects identical to that for an atom lacking 8 two d electrons from a completed d shell, i.e. a d configuration. Thus s Ni++, which has the configuration d has a set of atomic states arranged 2 3+ in Fig. 1115. Furthermore like those drawn for the d example of V
,
the crystalfield configurations will be the same except that we will be As a dealing, as it were, with positive holes in the completed d shell.
consequence, the ordering of the configurations with regard to energy The at the right of a diagram such as that of Fig. 1115 is reversed.
schematic energylevel diagram that would be drawn on this basis for Ni++ is shown in Fig. 1116.
In practice one does not encounter ligands that have a sufficiently strong crystal field completely to overshadow the electronrepulsion factors that operate in the atom to produce the different atomic states
TABLE 1111 Correlation of Atomic States, for Which Spherical Symmetry Exists, with the States Occurring in a Field of Octahedral Symmetry
Atomic
state
symbol
Alg
P D
F G
Tu
Ea + T H A 2a + Ti, + T 2g A le +Ea + T lg + T lg
299
for a given
number
of
electrons.
One
attention on the lefthand part of the diagrams that have just been discussed.
The
coordination chemistry,
shown
like
which is often studied in Here account is also quantummechanical states tend to "mix"
ion,
Ni ++
in Fig. 1117.
states
different
The schematic correlation diagram between the free ion and the strong
d8
ions.
Free ion
Strong
crystal field
electrons)
300
one another.
the two
3
is
1
T lg
energylevel lines.
Exercise 1111.
fields of
.
What
the energies of the configurations {h Y, (hgYieg) 1 {t2.g) l {e g y, and 3 Illustrate the answer by an energy diagram and show the energy (e g ) scale in terms of both the parameter A and the parameter 10D 9 Exercise 1112. Arrange according to energy, as in Exercise 1111, the
.
an octahedral complex.
it
energy states.
from the ground, 3 A 2g state, to the higherOne can immediately carry over the rule that forbids
FIG. 1117
symmetry.
state are
The energylevel diagram for a d 8 ion, such as Ni ++, in a field of octahedral The energies of the important states with the same multiplicity as the ground
lines.
shown as heavy
""
1
is
to
fit
Chemistry, "Methuen
&
(Ni(H 2 0) 6 ]
2!
/<V4
20,000
10,000
E u c
10,000
,)
20,000
<v
5,000
15,000
301
changes in the net spin of the system and can therefore, in this case,
expect the important spectral bands to be interpretable on the basis
'T ig state and the two 3 Ti g states. Furthermore, consideration of the transitionmoment integral leads to the conof the other triplet states, the
clusion, well
known
in
rule,
is
d orbitals are symmetric with respect to their origin, and since the dipolemoment term itself is antisymmetric, the product of the terms in the transitionmoment integral would be anti1112 shows,
all
symmetric and, therefore, according to the discussion of Sec. 45, the integral would necessarily be zero. For a coordination compound this rule is broken down, to some extent, because some of the vibrations
of the ligands with respect to the metal ion destroy the
symmetry
i.e.,
of the
system.
One
finds,
however,
that
dd
transitions,
transitions
between energy
tion
levels
absorption bands.
Typical values of
is
at the
maximum of the
absorp
band
"Wm^ =
ylog
(
j )
(10)
The corresponding
about 10~ 4
(It
should
Tranchanges lead, however, to very weak bands, with 7 and these are not generally observed when the / values of perhaps 10
sitions involving spin
,
much more
intense A<S
bands occur.)
the energylevel pattern for a given octahedrally coordinated metal ion can be used as a base for the interpretation of the observed
Now
The example of Ni++ is still suitable. The spectrum of the aquated ion [Ni(H 2 0)]++ is shown in Fig. 1118. The three absorption bands can be attributed to the states indicated above each absorption band, and the positions of these bands match up rather well with the
spectrum.
spacing between the energy levels of Fig. 1117
if
A =
8,500
cm
for the
[Ni(H 20)6]++
ion.
One final illustration of the crystal field interpretation of the delectron energy levels and the spectrum resulting from transitions between these levels can be given. The d* configuration, found in Mn++ and
Fe"11",
is
different
in
two regards.
is
First, for
(U
(e<,Y,
and
an energy that
302
of A.
e
state
shown
in Fig. 1119.
is
by any
of the
Although, to interpret the electronic spectrum, one would now normally focus one's attention primarily on the higher energy states with the same spin as the ground state, such states do not exist. The
highest spin found in the excited configurations corresponds to two
electrons being paired with opposite spins,
and this situation produces The energy levels for these states, states when radiation is absorbed
low crystal
is
shown
field
The spectrum
of
in line
with
First,
1119.
the low extinction coefficients, as compared for example with the cor
responding spectrum of the aquated Ni ++ ion, should be noticed. The oscillator strengths are less for Mn++ by a factor of about one hundred
and this can be attributed to the violation of the AS = rule that must accompany the dd transitions of the [Mn(H 2 0) 6 ++ ion. (The reader may, in fact, have noticed the generally pale colors displayed by manganese solutions, and this again can be attributed to the spin change involved in the visible region transitions.) The number and positions
]
of the absorption
bands
of various
Mn++ coordination
of
about 7,800
cm"
FIG. 1118
The absorption spectrum due to the octahedral ion [Ni(H 2 0)6] ++.
J.
[From
Chem.
Phys.,
8,000
12,000
16,000
20,000
24,000
28,000
303
50,000
<"V<V
2,500 5,000 7,500 10,000
12,500
A
FIG. 1119
state,
in
cm
1
1 1
The energylevel diagram for a a* 5 ion such as Mn" "" ". Only the ground designated as 6 S and e T ig and quartet states are shown. (From L. E. Orgel, "An
,
ltd.,
London, 1960.)
XinA
6,000
1
5,000
1
4,000
i
3,500
i
0.03
0.02
0.01 FIG. 1120 The absorption spectrum due to the ion [Mn(H 2 0) 6 ] ++ .
A^
20,000
An
1
30,000
25,000
><(cm _1 )
304
which predicts a group of three absorptions around 25,000 cm1 and another group of three around 30,000 cm 1 gives the best correlation between the energylevel diagram and the observed spectrum. The above examples illustrate the chief goals and results of the dis,
The
tude of
stood,
and the parameter A, measuring the magnithe interaction between the ligands and a metal ion, can be
Other spectra of other octahedral ions can also be underof A determined, from comparisons of the observed
In a similar
evaluated.
con
numbers
of
d electrons and can understand the principal feaFurthermore, other geometries, i.e.,
orbitals.
This ligand
field
approach
will not,
here.
Again
it
Although these bands are generally very intense, they usually occur farther out in the ultraviolet region than do the dd bands treated here.
They do
not,
it
highenergy electronic state have been dealt with in the preceding parts
ion,
Now we will investigate the ways in which a molecule, or can get rid of its excess energy and return to the ground state after Two general it has been raised to such a highenergy electronic state. types of energydissipation processes can be recognized. In one type,
of the chapter.
which we
energy
is
transferred to molecules
of this energy
away some
and
vibrational, energy.
No
emission of
305
radiation
processes,
is
of dissipation
on the other hand, involves an emission of radiant energy. Such radiation can be detected and analyzed, and as we will see, such
analysis leads to the further classifications of fluorescent emission
and
phosphorescent emission.
117.
Nonradiative Processes
As was discussed
in Sec. 101
and
band produces a higher energy electron configuration and often leaves the molecule in one of the
new electronic state. For molecules in appears that the molecular collisions are very effective in removing, probably by one vibrational level step at a time, the excess
higher vibrational states of the
solution
it
vibrational energy.
as emitted radiation.
When
this is
10~ 13
sec, it is
seen that
many
being
lost.
mechanism
down the
procedure
made
clear in the
effect a
slowing
down
under study in a solvent which, when cooled, One solvent often used is boric acid; another is a
mixture of ether, isopentane, and ethanol, referred to as EPA. The simple diagram of Fig. 101 showing the potential curve of
the ground electronic configuration
configuration
is
and that
molecules and is inadequate for a complete discussion of radiationless energy dissipation. A number of different electronic configurations
must be expected to have energies that lead to potentialenergy curves by this diagram. In this regard Fig. 1020 is more typical. Furthermore, the potential energy for a given electronic
in the region covered
and
would have to be
represented
by a
The
net
two
features
is
or,
more
properly, surfaces of different electronic states will cross one another, and
is
initially
radiationless process.
excited molecule to
ground
When two potential surfaces or, state. two potential curves cross as in Fig. 1121,
tion corresponding to the curve labeled S, to change over into the configuration corresponding to the curve labeled S'.
The
crossing of the
known
as internal conversion,
FIG.
1121
Ground
307
because at the crossover point the potential energies of the two electronic states are equal and the vibrational kinetic energy of the molecule in
would be zero. For polyatomic molecules, potential curves often exist with suitable relative positions so that combinations of vibrational deactivations and internal conversions can return the molecule to its ground state Other molecules, before any emission process has had a chance to occur. curves or have potential however, either do not have such crossing
either state
which the molecule becomes trapped. In such cases emission does occur, and we will now investigate how this happens.
electronic states in
118.
Fluorescence
If
the efficiency of internal conversion processes that return the molecule to its ground state is not too great, various emission processes
can occur.
The
simplest
mechanism that
in Fig.
is
consistent with
observed emission
is illustrated
1122.
the emission band generally appears at longer wavelengths, i.e., lower energy, than the absorption band suggests that vibrational deactivation
within the potential curve of the upper electronic state
is
essentially
FIG.
122
same
reached by the
excitation process.
308
complete before
transition,
much
transition of Fig. 1122, rather than the exact reverse of the absorption
is
to be
drawn.
illustrate this
Since most fairly intense absorption bands that are observed occur from the ground state to an excited state with the same multiplicity as the ground state, the emission process of Fig. 1122 is a transition with no multiplicity change. It is now becoming customary, although other conventions are used, to use the term fluorescence for emission transitions that occur between states of the same multiplicity. This definition includes, therefore, emissions from states reached from the initial excited state by internal conversion as long as the second state has the same multiplicity, usually a singlet state, as the ground state.
We
will
now
and
(Transitions
process
is
ended.)
FIG. 1123
in
dionane showing the occurrence of the emission band at longer wavelengths, as suggested by the transition arrows of Fig. 1122. [From G. Kortum and B. Finckh, Z. physik Chem.
B52, 263 (1942).]
XA
5,000
1
4,000
1
3,000
1
Absorption
/ Emission
20,000
22,000
24,000
26,000
28,000
30,000
32,000
309
Let us now consider the rate, or probability, for an emission process the type illustrated in Fig. 1122. The experimental results that of might try to understand would consist of measurements of the one
change of intensity of the emitted radiation with time after the radiation
beam
been turned
Information
is
spontaneous emission.
coefficient of
show that a
it is
coefficient
related to the
4.
We
state designated as h.
containing these molecules to be in a blackbody cavity in which the radiation density p(v) is related to the frequency and the temperature
by Planck's
, .
radiation law
P()
= 0 e h,lkT _
8whv"
11A (")
At equilibrium the
ratio of the
number
g
of molecules
in the higher
in the
ground state
will
be given by
Boltzmann's distribution as
Ei.
e,rt /*r
(12)
is the energy difference, per molecule, between the two states. must investigate the mechanism by which this equilibrium is established and maintained. Molecules can be excited from state g to state h by transitions induced by the radiation in the cavity. Recalling the Einstein coefficient of induced absorption B g h introduced in Eq. (35) of Chap. 4, one writes
where hv g h
Now we
Rate
of g
h transitions
N B ^hp{y
g
g h)
(13)
Transitions
taneous emission.
downward can occur by either induced emission or sponOne can write the net rate of these processes as
h
Rate
of
>
g transitions
iV\[.B*. p(>',,iO
+A
h > g ]
(14)
where Ah* g
of
is
will be determined by relations established here. however, from the discussion of Chap. 4 that B g , h = B h, g .)
A h,g
310
rates
N
Now
tity,
B^ gP
Vgh )
+ A^
one can replace N h /N a by the Boltzmann expression for this quanand one can also replace p{vhg ) by the blackbody expression of Eq. (11). Rearrangement of the resulting equation gives, with
_
=
8rh(v gh )*
C3
8irh(v gh ) 3
B ^h
g
(16)
We
absorption band,
.
by Eqs.
(36)
and
(46) in
Chap.
4.
Thus
"
_ ,
64r(iv)'M,
3h
8,(l,000)cft0 '
J
With
this result, the value of
g(f) d v
(17)
A h^g
The
time
it
lifetime of
is
exciting radiation
an excited state that spontaneously emits after the turned off can be calculated as a half life, i.e., the
rate equation
or
(18)
d In
=  (A k^g )
dt
I
to
t\
in
which
goes from
to
iNh
gives
or
'*
(19)
In 2
AT~
311
A h ^g
gives
h =
2Vln2
8irc(l,000)(P) 2 /a(P) dv
0.55
2
10"
(iVJk)
/a(P) dv
(20)
Alternatively one can relate the halflife to the oscillator strength / If one inserts the relation of of the transition discussed in Sec. 49.
4,
one has
<21 >
<S?
A
typical strong absorption
band due to an allowed electronic band maximum at, perhaps, 3,000 transition has }a(v) dv 1 The emission from the excited state reached by this A, or 30,000 cm
10 9 and a
halflife,
due
10"
10 8 (10 9 )
Q 6
10
_9
gec
(22)
Such
section.
lifetimes are
comparable with, or shorter than, typical nonthat any decrease in the efficiency of
freezing in a glass or cooling to liquid
collisional deactivation, as
by
Many
i.e.,
allowed transitions.
view of Eq.
(20),
One
finds in
much
Ah,,, is
Phosphorescence
is
Phosphorescent emission
states with
primarily as a result of
momenta. It is now recognized, the early work of G. N. Lewis, that the most
312
important phosphorescent bands of organic compounds arise from transiand a singlet ground state. The potentialenergy diagram that represents a situation that can
lead to phosphorescence
is
shown
in Fig. 1124.
singlet
Absorption of radiation
singlet to
an excited
extent; i.e., the transition can be allowed. Collisional deactivation can then drop the energy past the point where the potential curve of the
singlet state crosses that of the triplet state.
if the not carry the molecule too quickly past the Once a triplet electronic state is formed,
tripletstate molecules
further vibrational energy will be lost and the molecules will occupy
ground
by the pro
124
singlet
S and
triplet
T states that
^___
'
S'
\
\
>v
\
*.y
/ \/
/
>^_^/\s.
^
'
'/
Representative coordinate
313
occur with low probability, i.e., a will be very small, and the phosrelatively long periods of time. continue over phorescent emission will
Halflives for phosphorescence of the order of seconds, or longer, are not
A^
uncommon.
(One should recognize that the relation between the ,& and Aj_ coefficients and the relation between A h + g and ij require a roundabout mechanism, such as that of Fig. 1122, in order to populate
a longlived excited state.)
The
state
is
and a
triplet
even
if
is seldom observed in liquids at ordinary temperatures. Again the process of forming a glass with the material as a solute and cooling the system to liquid nitrogen temperatures is often resorted to. With this procedure many organic compounds undergo appreciable
phosphorescence
system crossing, and are observed to emit radiation as phosphorescence. It should be mentioned that the lifetimes of excited states is a
subject of great importance in photochemical studies.
The occurrence
phosphorescence, often provides the means whereby photochemical reactions can occur.
ticularly
In this
fluorescence
way the study of electronic spectra, and parand phosphorescence, and photochemistry are
intimately related.
INDEX
Absorption
coefficient,
70^71
Bond
cules,
114
7476 for vibrational transitions, 7680 Amplitudes of vibration, 32 for spring systems, 116122
for particleinabox model,
in linear molecules, 57 in
145
Angstrom
unit, 9
Broglie, L. de, 11
quantum
Centralforce
field,
204, 205
energy levels
structures
of,
of,
rotational spectra
of,
109112 112114
114
Character table, 168171 Characters of representations, 183186 Chargetransfer transitions, 288 Classes, in group theory, 186188 Configurations, electronic, in atoms, 247 in molecules, 251260, 267269, 284 Conjugated systems, 276278
normal, 116122
B,B, definition
of,
ultraviolet
spectrum
of,
279286 286
symmetry, 215, 216 Coordination compounds, 288312 Correlation diagrams, 257259 Coupling of rotationvibration, 138141
Crystalfield theory, 288
Bohr, N., 8
Bohr hydrogen atom model, 811 Bohr orbits, 9 Boltzmann distribution, 23, 24
for rotational for vibrational
d orbitals, 290 Davisson and Germer, 11 Degeneracy, 11 Degenerate vibrations, 129, 130
315
316
Degrees of freedom, vibrational, 115, 116 Deslandres table, 234238 Diatomic molecules, electronic states of, 230263 rotation of, 4760 rotationvibration bands of, 134142 vibration of, 2546 Dipole moments, from rotational spectra, 9092 table of, 92 Displacement coordinate, 27, 208, 209 Dissociation energy, 35, 237, 238
oscillator strength, 81
statistics, 100,
FermiDirac
145
HC1, 42 204206
table of, 42
FranckCondon
Frequency,
Eigenfunction, 12, 13, 16 Einstein, A., 8
Einstein's coefficient, of induced absorption,
principle,
233
69
G matrix,
on energy
levels,
89
of electromagnetic radiation, 4
198200
Electromagnetic radiation, interaction with molecules, 6670 regions of, 5 Electron spin resonance spectroscopy, 3 Electronic configurations, for atoms, 247 for benzene, 284 for carbonyl group, 267269 for diatomic molecules, 251260 Electronic orbitals, in aromatic systems,
Harmonic
oscillator,
quantum mechani
3739 Hermite polynomial, 39 Hexatriene, 17 Hooke's law, 27, 28, 31 Hund's rule, 248, 271
cal solution for,
279282
276279 in coordination compounds, 289293 in diatomic molecules, 251260 Electronic spectra, of benzene, 286 of carbonyl compounds, 272 of coordination compounds, 302, 303 of diatomic molecules, 231244 Electronic states, of atoms, 244251 of benzene, 279286 of carbonyl compounds, 269271 of coordination compounds, 293304 of diatomic molecules, 260261 Electronic transitions, intensities of, 8081
in conjugated systems,
Kinetic energy, of a rotating molecule, 49, 104, 109 of a vibrating molecule, 263
of a vibrating particle, 29
Emission, 304313
Lagrange's equation, 29, 31, 207, 208 Laporte rule, 301 Ligandfield theory, 289 Linear molecules, rotation of, 5060 rotationvibration bands of, 142149 rotational selection rules for, 8489
INDEX
317
8992
76
Telectrons, 16
Molecular orbitals for benzene, 281282 Moment of inertia, 48, 49 for excited electronic states, 238243
of rotational levels, 53
Newton's equation, 12
Nonbonding
orbitals, 267 Nonradiative processes, 304307 Nonrigid rotor, 5760 Normal coordinates, 116122, 202 of a linear triatomic molecule, 212 symmetry of, 125130 Normal modes, symmetry of, 194195 Normal vibrations, 116122
Quantum
restrictions, 7
Oblate symmetrictop molecules, 105 Octahedral symmetry, 290 Octatetraene, 276278 Operators, 2123 table of, 22 Ortho states, 102 Orthogonality of wave functions, 18, 19
Oscillator strength, 81
179183
Overtones, 45, 46
Para
states,
102
146
of
Pauli exclusion principle, 100 Perpendicular bands, of linear molecules, 146149 of symmetric top molecules, 152158
Rigid rotor, 47 Rotation, of a linear system, 4852 of symmetric top molecules, 103109 Rotationvibration spectra, of diatomic molecules, 134142 of linear molecules, 142149 of symmetric top molecules, 149158 Rotational energies, of asymmetric top molecules, 113 of linear molecules, 50, 51 of symmetric top molecules, 103109 Rotational selection rules, 8489 Rotational structure of electronic bands, 238244
318
Thomson,
J. J.,
moment, 69
spontaneous, 307312
Ungerade
vibrational, 40, 41 Separated atoms, 252, 253 <r bonds, 266, 267 Spectrometers, 2 Spontaneous emission, 309311 Stark effect, 8992 Statistical weight of rotational levels, 98103
Valenceforce
field, 205 Vector model of the atom, 249251 Vibrational energies, of diatomic molecules, 2546 of polyatomic molecules, 122124, 203206
114
of linear molecules, 57
of,
76
80
Vibrations, classical, 2634
of
rotation
of,
103109
0, 214218
208212
vibra
213218 of degenerate vibrations, 129, 130 of electronic states, 269271 of normal coordinates, 125130
in vibrational calculations, 213218,
Wave Wave
for
equation, 12
functions, for atomic orbitals, 86
harmonic
oscillator,
39
244
226, 229
method
tions,
218229
Other McGrawHill
4> 99 99
Related Fields
Ed
3
as
Physical Chemistry Organic Chemistry, 2nd Ed. Eiperimental Physical Chemistry. 6th Ed Physical Chemistry of Metals Instrumental Methods of Chemical Analysis. 2nd Ed Fundamental Concepts ol Inorganic Chen
iiiclear Pliv
Scientists
And Engini
Ed
fundamentals
of Electricity
and Magnetism
w o c >
99
(It
PAULING
Introduction to
Quantum Mecha
for
0
Physicists,
Engineers and
2nd Ed.
Modern
Quantum Mechanics, 2nd Ed he Modern Theory of Solids Chemistry. 2nd Ed Electromagnetism Modern Physics Mathematics of Physics and Modern Engineering
Principles of Mechanics, 3rd Ed. College Physics, 3rd Ed.
n 9
99
SYNGE WEBER
WHITE
O cn o o
Production to Atomic Spectra Principles of Biochemistry. 2nd Ed. ieat and Thermodynamics. 4th Ed.
Muito mais do que documentos
Descubra tudo o que o Scribd tem a oferecer, incluindo livros e audiolivros de grandes editoras.
Cancele quando quiser.