Degrees of Freedom

Rotational Spectroscopy
Electronic Transitions
Vibrational Spectroscopy
microwave
infrared
Interaction with matter Energy levels
Spectroscopy
Absorption Spectroscopy Emission Spectroscopy
Introduction to Spectroscopy

Rotational Spectroscopy

Vibrational Spectroscopy

Absorption and emission Spectroscopy
Lakowicz, Principles of Fluorescence Spectroscopy, Springer Publishers, 3rd Edition, 2011
Atkins, Physical Chemistry, 9th edition, 2009
Banwell & McCash, Fundamentals of Molecular Spectroscopy, 4th edition, 1996
Moog, Spencer and farrell, Physical Chemistry: A Guided Inquiry: Atoms, Molecules,
and Spectroscopy, 2003
The sun produces a full spectrum of electromagnetic
radiation
http://csep10.phys.utk.edu/astr162/lect/light/spectrum.html
http://kr.blog.yahoo.com/bmw26z/2188
Components of Electro Magnetic
Radiation
v
Two Components of EM
Radiation
Electrical field (E): varies in magnitude in a direction
perpendicular to the direction of propagation
Magnetic field (M): at right angle to the electrical
field, is propagated in phase with the electrical field
Wavelength (), distance from one wave crest to another
Frequency (v), No. of crests passing a fixed point/ given time
Amplitude, height of each peak (watts/sq. meter
The speed of EM energy c 300,000km/second,
c = v where and v are inversely related

Interaction of radiation with matter
If there are no available quantized energy levels matching the quantum
energy of the incident radiation, then the material will be transparent to that
radiation
Wavelength
Fate of molecule?
Non-radiative transition: M* + M M + M + heat
Spontaneous emission: M* M + hv (very fast for large
AE)
Stimulated emission (opposite to stimulated absorption)

These factors contribute to linewidth & to lifetime of excited
state.
Molecular Motion and Spectroscopy

Study of Interaction of Matter and Light (Photon)

Molecular Spectroscopy
Information about molecules such as geometry and energy
levels are obtained by the interaction of molecules and photons
Molecular motions: Translation, Rotation, Vibration
determines the energy levels for the absorption or emission of
photons
Electronic, Vibrational, and Rotational Energy Levels
of a Diatomic Molecule
Exercise: Indicate the
molecular state in which it is
electronically in the ground
state, vibrationally in the first
excited state, and rotationally
in the ground state.
ROTATIONAL
SPECTROSCOPY
Microwave interactions
Quantum energy of microwave photons (0.00001-0.001 eV) matches the ranges
of energies separating quantum states of molecular rotations and torsion

Note that rotational motion of molecules is quantized, like electronic and
vibrational transitions associated absorption/emission lines

Absorption of microwave radiation causes heating due to increased molecular
rotational activity
Molecular rotations
Types of Rigid Rotors
A schematic illustration of the
classification of rigid rotors.
A diatomic molecule can rotate
around a vertical axis. The
rotational energy is quantized.
RIGID ROTOR
Figure 40-16 goes here.







THE RIGID ROTOR

A diatomic molecule may be thought of as two atoms held
together with a massless, rigid rod (rigid rotator model).


o
r
1
| r
2

m
1
m
2
o
Consider a diatomic molecule with different atoms of mass
m
1
and m
2
, whose distance from the center of mass are r
1
and
r
2
respectively
The moment of inertia of the system about the center of
mass is:

I = m
1
r
1
2
+ m
2
r
2
2
The Definition of Moment of
Inertia
In this molecule
three identical atoms
attached to the B atom
three different but mutually
identical atoms attached to
the C atom.
Centre of mass lies on the
C
3
axis
Perpendicular distances
are measured from the
axis passing through the B
and C atoms.
Rotational levels
) 1 (
2

2 2
2
2
2 2
+
|
.
|

\
|

= = =
J J
h
L
momentum angular L where
I
L I
E
r
t
e
The classical expression for energy of rotation is :In the
harmonic oscillator model, the energy was all potential
energy. In the rigid rotor, its all kinetic energy:

where J is the rotational quantum number
constant rotational the
8
) 1 ( ) 1 (
2 2
1
) (
2
2
I c
h
B
J J B c h J J
h
I
J E
t
t
v
v
=
+ = +
|
.
|

\
|
=
Quantization of Rotational Energy
2
( )
8
h
B
cI t
=
V = 0
cyclic boundary condition: (2 + ) = ()
By solving Schrodinger equation for rotational motion
the rotational energy levels are
Rotational energy levels in wavenumber (cm
-1
)
Spacing between adjacent rotational levels j and j-1)
The Gross Selection Rule for
Rotations
A rotating polar
molecule looks like
an oscillating dipole
which can stir the
electromagnetic field
into oscillation.
Classical origin of
the gross selection
rule for rotational
transitions.
/ h hc c v A = =
1
1 ( )
1 ( )
j
j absorption
j emission
A =
A = +
A =
Rotational Spectroscopy
(1) Bohr postulate
(2) Selection Rule
ROTATIONAL SPECTRUM
Selection Rule: Apart from Specific rule- AJ= 1, Gross
rule- the molecule should have a permanent electric dipole
moment, . Thus, homonuclear diatomic molecules do not
have a pure rotational spectrum. Heteronuclear diatomic
molecules do have rotational spectra
1
1 ( )
1 ( )
j
j absorption
j emission
A =
A = +
A =
Appearance of rotational spectrum We can calculate
the energy corresponding to rotational transitions

A E=E
J
E
J
for

Or generally:
J J + 1 = B(J+1)(J+2) - BJ(J+1)

= 2B(J+1) cm
-1

Microwave absorption lines should appear at

J = 0 J = 1 : = 2B - 0 = 2B cm
-1

J = 1 J = 2 : = 4B cm
-1


Note that the selection rule is AJ = 1, where +
applies to absorption and - to emission.

1 + = = A
initial final
J J J

Relative Intensities of rotation spectral

lines
Now we understand the locations (positions)
of lines in the microwave spectrum, we can
see which lines are strongest.

J BJ(J+1)

J=0 0

Intensity depends upon two factors:
Intensity depends upon two factors:
1.Greater initial state population gives stronger spectral
lines.This population depends upon temperature, T.


k = Boltzmanns constant, 1.380658 x 10
-23
J
K
-1

(k = R/N)


We conclude that the population is smaller for
higher J states.
|
.
|

\
|
=
|
.
|

\
|

kT
hc
exp
kT
E
exp
N
N
J
0
J
cmK 1.52034
k
hc
=
|
.
|

\
|

T
1.52034
e
N
N
o
J
2. Intensity also depends on degeneracy of initial
state.

(degeneracy = existence of 2 or more energy states having exactly
the same energy)
Each level J is (2J+1) degenerate
population is greater for higher J states.
To summarize: Total relative population at energy
E
J
o (2J+1) exp (-E
J
/ kT) & maximum population
occurs at nearest integral J value to :

Look at the values of N
J
/N
0
in the figure, .

Plot of population of rotational energy levels
versus value of J.
B = 10cm
-1
max.
pop.

J
0
P
o
p

o

(
2
J

+

1
)

e

(

-
B
J
(
J

+

1
)
h
c
/
k
T
)

MCWE or Rotational Spectroscopy
Classification of molecules
Based on moments of inertia, I=mr
2

I
A
= I
B
= I
C
very complex eg H
2
O
I
A
= I
B
= I
C
no MCWE spectrum eg
CH
4

I
A
= I
B
= I
C
complicated eg NH
3
I
A
= 0, I
B
= I
C
linear molecules eg: CO
( )
E
J J
I
J M J
J J
=
+
= =
1
2
0 1 2 0 1
2

with also , , , , ,

Vibrational Spectroscopy


Vibrational Spectra
Molecules are not Static
Vibration of bonds occurs in the liquid, solid and gaseous phase
Vibrating Energy Frequency (and the appropriate frequencies
for molecular vibrations are in the Infrared region of the
electromagnetic spectrum
Vibrations form therefore, a fundamental basis for spectroscopy in
chemistry--the bonds are what makes the chemistry work in structure
and function
For Organic Chemistry the most important uses of these vibrations is
for analysis of:
functional groups
structural identity, fingerprinting
What Kind of vibrations are These?
Bonds can.
Stretch
Bend
Wag
(rock)
These can number into the
hundreds.
Some are symmetrical, some
antisymmetrical and many are
coupled across the molecule
Can be calculated. One easy
approximation is:

k
12
10 3 . 5

=
2 1
2 1
m m
m m
+
=
The reduced mass where m
1
, m
2

are the masses on either side of
vibration
k is the force constant, like the
Hookes Law restoring force for a
spring. Known and tabulated for
different vibrations
The Fundamentals
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
antisymmetric symmetric
rocking scissoring
in-plane
bending
stretching
out-of-plane
bending
wagging twisting
These oscillating electric
dipoles match in frequency
the incoming e-field
oscillations of IR light.
All the simple possibilities.
For n atoms in a molecule;
Linear: 3n 5 modes
Non-linear: 3n 6
modes
Example for a
methylene,given n=3
While useful, this
oversimplifies, since
molecular orbital picture
requires that atoms cant
vibrate without affecting
the rest of the molecule.
Vibrational Motion: Molecular Calisthenics
Harmonic oscillator
( )
e
F k r r =
14
1
2 10
vib
s t
v

= ~
A molecule vibrates ~50 times
during a molecular day (one rotation)
Quantization of Vibrational Energy
By solving Schrodinger equation for vibrational motion,
Vibrational energy level
Zero point energy
Spacing between adjacent vibrational sates
where is a vibrational quantum number
A Functional Group Chart
O-H str
NH str
COO-H
=C-H str
C
sp3
-H
C-H
-(C=O)-H
CN
CC
C=O
-C=N
-C=C
phenyl
C-O
C-N
F C-X
4000 3600 3200 2800 2400
2000 1600 1200 800 group
Br
Cl
Regions of Frequencies
Near -to
visible- IR
(NIR)
Combination
bands
3.8 x 10
14

to 1.2
x 10
14

12800 to 4000 0.78 to 2.5
Mid Infrared
Fundmental
bands for
organic
molecules
1.2 x 10
14

to 6.0
x 10
12


4000 to 200 2.5 to 50
Far IR
Inorganics
organometallics
6.0 x 10
12

to 3.0
x 10
11


200 to 10 50 to 1000
Spectral Region Frequency(Hz) Wavenumber(cm
-1
) Wavelength (,m)
Looking at a Spectrum
Divide the spectrum in to two regions:
4000 cm
-1
1600 cm
-1
most of the stretching bands,
specific functional groups
(specific atom pairs). This is the
functional group region.

1600 cm
-1
400 cm
-1
Many band of mixed origin. Some
prominent bands are reliable. This
is the fingerprint region. Use
for comparison with literature
spectra.

Wavenumber is cm
-1
=10
4
/()
What kinds of Bonds Absorb in
which Regions?
Bending is easier than stretching-- happens at lower energy
(lower wavenumber)
Bond Order is reflected in ordering-- triple>double>single (energy)
with single bonds easier than double
easier than triple

Heavier atoms move slower than
lighter ones
The k in the frequency
equation is in mDyne/ of
displacement
Single bond str 3-6 mD/
Double bond str. 10-12 mD/
Triple Bond 15-18 mD/
Effects of conjugation
Lowers to
1715 cm
-1
Similar, to
1715 cm
-1
Raises to
1770 cm
-1
:

Weakens DB
character
Strengthens DB
character (inductive
over resonance)

Degrees of Freedom:
Translation, Rotation, and Vibration






Consider a single Ar atom moving in 3-D space:

- Moving motion is referred to as Translation
- To analyze the translation of an Ar, we need to know
position (x, y, z) and momentum (p
x
, p
y
, p
z
)
Where it is Where it is headed

- Each coordinate-momentum pair [for example, (x,p
x
)] is
referred to as a Degree of Freedom (DF)

- An Ar atom moving through 3-D space has three DFs

N argon atoms possesses 3N DFs:
All translational DFs
Center of Mass (Balanced
Point)
- A point mass that can represent the
molecule
- Motion of the center of mass requires 3 DFs
to describe it
- In general, regardless of its size or
complexity, a molecule has 3 translational
DFs
- Thus, (3N 3) DFs for the internal motions
of rotation and vibration
Rotational and vibrational
DFs
N atomic
Linear
Molecule
N atomic
Non-Linear
Molecule


Rotation

2 DFs

3 DFs

Vibration

3N 5

3N - 6

Vibrational Spectroscopy
Vibrational selection rule
1
1 ( )
1 ( )
absorption
emission
u
u
u
A =
A = +
A =
The Vibrations of CO
2
.
The stretching modes are not
independent, and if one CO
group is excited the other begins
to vibrate.
The symmetric and
antisymmetric stretches are
independent, and one can be
excited without affecting the
other: they are normal modes.
The two perpendicular bending
motions are also normal modes.
The Normal Modes of Water
The three normal
modes of H
2
O. The
mode v
2
is
predominantly
bending, and occurs
at lower
wavenumber than
the other two.
Absorption and Emission Spectroscopy
Electronic Transitions in Molecules
Molecular Orbital (MO) Theory
for C
2
H
4
molecule,
UV or Visible
spectral region
Department of Chemistry, KAIST
Fate of Excited Electronic States
Reflection and Scattering Losses
Introduction to Absorption
LAMBERT-BEER LAW
ion concentrat
pathlength
ty absorptivi
log log
0
0
=
=
=
= =
|
|
.
|

\
|
= =
= =
c
b
a
kc abc A
P
P
T A
P
P
P
P
T
solvent
solution
Power of
radiation after
passing through
the solvent
Power of radiation
after passing
through the sample
solution
Beers law and mixtures
Each analyte present in the solution absorbs light!
The magnitude of the absorption depends on its c
A
total
= A
1
+A
2
++A
n
A
total
= c
1
bc
1
+c
2
bc
2
++c
n
bc
n
If c
1
= c
2
=

c
n
then simultaneous determination is
impossible
Need ns where cs are different to solve the mixture

Molecular Transitions
for UV-Visible Absorptions
What electrons can we use for these
transitions?
Spectral nomenclature of shifts
Introduction to Emission
Luminescence: emission of photons from
electronically excited states of atoms,
molecules, and ions.
Fluorescence: Average lifetime from <10
10

to 10
7
sec from singlet states.
Phosphorescence: Average lifetime from 10
5

to >10
+3
sec from triplet excited states.
Importance of Emission
Spectroscopy
Sensitivity to local electrical environment
polarity, hydrophobicity
Track (bio-)chemical reactions
Measure local friction (microviscosity)
Track solvation dynamics
Measure distances using molecular rulers:
fluorescence resonance energy transfer (FRET)
Photophysics: Jablonski Diagram
Kashas rule, Internal Conversion, Intersystem crossing, fluorescence, phosphorescence
Principles
Interaction of photons with molecules
results in promotion of valence electrons
from ground state orbitals to high energy
levels.
The molecules are said to be in excited
state.
Molecules in excited state do not remain
there long but spontaneously relax to more
stable ground state.
The relaxation process is brought about by
collisional energy transfer to solvent or
other molecules in the solution.
Some excited molecules however return to
the ground state by emitting the excess
energy as light.
This process is called fluorescence.
Light Amplification by Stimulated Emission of Radiation
In a laser.
Three key elements in a laser

Pumping process prepares amplifying medium in suitable state
Optical power increases on each pass through amplifying medium
If gain exceeds loss, device will oscillate, generating a coherentoutput