Escolar Documentos
Profissional Documentos
Cultura Documentos
II
The introduction of essentially nonmathematical descriptions of molecular orhital theory into the chemical
curriculum a t a very early stage makes it desirable to give
a comparable description of hyhrid atomic orhitals a t
about the same time and a t about the same level. Excellent elementary quantum mechanical treatments of hybridization are available (1-6) and several authors have given
quite satisfactory treatments which require relatively little knowledge of quantum mechanical theory (7-9) However, these treatments require some group theory hackground, which although relatively easy to master, is not a t
the disposal of the student when he usually first encounters hybridization.
Students are introduced to descriptions of orhitals very
early in their careers. The angular distribution of the 2p
atomic orhital in the form of a figure 8 is already familiar
to a second year student. What perhaps is not appreciated
is that an orhital is in fact a description of a wave function. What the student should now he taught is the form
of the wave function which corresponds to the orbital displayed. In the case of the pure p atomic orbital this presents no special problem' hut the correspondence between
a hyhrid orhital and the complete analytic form of the
wave function it represents may present some difficulty.
In the first portion of this aiticle we wish to point out
that equivalent sets of hybrid atomic orbitals may he generated by a very simple geometric construction method.
This construction method will lead by inspection to the
correct assignment of algebraic signs and when combined
with the simple arithmetic requirements of orthonormal
sets, the method leads immediately to a correct set of hybrid orbitals or, more exactly, to the correct wave functions which these orbitals represent. The arithmetic depends on the application of three basic requirements of
wave functions.
( 1 ) Normalization. Assume that we are dealing with one
of the three familiarly shaped sp2 hyhrid atomic wave
functions consisting of one part s orbital and two parts p
orhital. Assume the particular hybrid orhital, 4,, has the
form
114 /Journal
of Chemical Education
(3) Unit Orbital Contribution. The squares of the coefficients of any one component atomic wave function
summed over all the hybrids in which it participates must
be equal to unity, i.e.
In the first portion of this paper we will consider equivalent hybrid wave functions made up of va~iousmixtures
of s and p orhitals all of which have the form
d, = c,l(s) + c&J
+ C ~ P +Jc , r ( p , )
(ma
The three other sp3 hybrid orbitals 42, 43, and b4 are all
equivalent with respect to the z axis. The coefficients of
p, for these three hybrid orbitals can then be obtained
from the unit orbital contribution requirement
m3 and $4
whence
and
The calculation of the coefficients of p, in the hybrid orbitals $3 and $4 is straightforward. Since both the hybrid
orbitals are equivalent with respect to t h e y axis and according to Figure 2 have opposite signs, ca3 =
and
c43 = The resulting hybrid orbitals are
v'w
and
A more common orthonormal set of tetrahedral sp3 hybrid orbitals is obtained if the orientation of the hybrid
orbitals and the coordinate system are specified as shown
in Figure 3. This figure shows that all four hybrid orbitals
Volume 50, Number 2. February 1973 / 115
Figure 3. schematic diagram showing the four hybrid sp3 orbitals equivalent with respect to three coordinate axes.
zA
@)- f%"-:~l")
@$
0.255 -0.437 -0.163
0.952
-0.45% 0.952 0.544 -0.43i
Steo 1. Snecifv
. the four atomic orbitals in the cartesian
coordinate system as shown in Figure 4.
Step 2. Each of the four equivalent dsp2 orhitals receives a contribution of one-fourth of the s orbital, thus
the coefficient of the s orbital in each hvbrid orbital is
112.
a2, ( ~ + p . - p ,
- p ~ + %2 ? ( s - p ~ + p , - p J
fi
For $n it is only necessary to change the sign of the coefficient of thep, component in $3
3 s + - p2l
a,,
+ a,, + a , ,
g,(dspq
+ a,,
116 /Journal
of Chemical Education
+ fl
1
a,, = a,, = --- = 0.633
4
1- fi
als = a , , = ----- = -0.183
4
a,, - a,, =
+ n,, = I
Ls
= 2
4.b%
xL
dr2
dx7,7
d%p3
- Y
F i u r e 5. Schematic diagram showing the six d2sp3 hybrid orbital9 from 4s. 40,.
3d,2 and 3d,2
.z component orbitals.
4p,, 4p,.
c,.,~
In the hybrid orbital 62(sp2) above, for example, the contribution of the s component orbital is (d/3)2= 113,
while the total contribution of the p component orbital is
leading to an orbital consisting of 113 s and 213 p character respectively. The other two orbitals likewise have this
character and all three sp2 hybrids may be written
% s Character
Accordingly, 4~ and 46 are given by
X' X 100
Thus far we have considered only equivalent hybrid orbitals; such orbitals are present when all the atoms bonded to the central element in question are equivalent such
as the three .sp2 hybrid orbitals of the boron atom in BFs
and the four sp3 orbitals of the carbon atom in CH4 or
CClr. If the element is involved in bonding with nonequivalent atoms, the orbitals involved need no longer he
equivalent. We saw above, that the amount of p character
may be calculated from a bond angle. For two equivalent
hybrid orbitals, i, eqn. (1) is
117
unhybridired
P
hybridized
........-
~ ->
&
1
= 0.60
Jfi0.57
=
whereas for two different hyhrid orbitals, i, and, j, separated by an angle mij, the equation becomes
m 2 ( s ~ ~ -=' ~
) + 0.71py - 0 . 4 2 ~ ~
0.57s
~ 0.42pn
~
$ ~ ( . F P ~=. '0.57s
~) - 0 . 7 1 Summary
The analytic form of sets of equivalent hyhrid orbitals
can be readily obtained by drawing these orbitals in a
conveniently chosen coordinate system and then applying
the arithmetical requirements for correct sets of atomic
hybrid wave functions, i.e., normalization, orthogonalization, and unit orbital contribution. The method is illustrated for sp2, sp3, dsp2, and d2sp3 hybrid orbitals.
This procedure is also applicable to sets of nonequivalent hyhrid orbitals; the hybrid atomic orbitals of carbon
in formaldehyde are derived as an example. Finally, given
the hybridization index of an atomic orbital, its analytic
form is obtained by use of the same principles. Thus, for
example, the sp1.77 atomic hybrid orbital of carbon in
formaldehyde is shown to correspond to 0.60s 0.80pZ.
Acknowledgment
(81 Cotton. F. A,, "Chemical Application of Group Theory." (2nd Ed.1. lnterseknreJohn Wiley, NewYork.
1971.
191 Murrcl. .J. N., Kettle. S. F. A,. and Tedder. .J. M.. "Valence Theory," John Wiiey
XI snn. MewYnrk
I~
S.
6~..
~~~,
(10) Mislow. K.. "Intmduetion to Stercochemiatry," W. A. Benjamin. Inc.. New York.
1965; Hendricluan, J. 8.. Cram. D. J., and Hamrnond. G. S.. "Oieanic Chemir~
whereupon
118 /Journal
I9i1951l.
of Chemical Education