*
99
O
o
>
M O*
weo
•a
wff.
oo
H»
*S
o
introduction to
MOLECULAR
4
SPECTROSCOPY
G. M. BARROW
kctwiHi
Ccu U.C.
//<»
/">
Introduction to
MOLECULAR SPECTROSCOPY
ufY^/^Mr^f*"
n n np (P*
Introduction to
M O L u
GORDON M. BARROW
Professor of Chemistry
Case Institute of Technology
I96L
INTRODUCTION TO MOLECULAR SPECTROSCOPY
tool, but should also provide that comfortable feeling of knowing "what
is happening" when spectroscopic techniques, or results obtained by these
techniques, are used.
No special background is necessary for the study of this book.
Although the Schrodinger wave equation is introduced and simple prob
lems to illustrate its relation to quantities that are important in spectros
copy are solved, no prior knowledge of quantum mechanics is assumed.
In a similar way, some of the theory known as "group theory" is given
and some analyses are based on the methods of group theory. Again no
previous knowledge of this subject is necessary. The use of quantum
mechanics and group theory is carefully confined to areas of specific value
in this introduction to spectroscopy. The level of treatment is main
tained by avoiding the many additional avenues that these subjects
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
ized reference books and the research literature of molecular spectroscopy.
In fact the goal of much of the material presented could be considered
to be that of providing readier access for the student to the 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 coordi
nation compounds that are now being based, to a large extent, on spectros
copic results. The organic chemist, to use a specific example, should
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,
of course, considerable in a book which attempts to serve as an introduc
tion to a field as extensive as spectroscopy. Judgement as to the relative
Gordon M. Barrow
CONTENTS
Preface v
INTRODUCTION
Classifications of Spectroscopy 1
Index 315
INTRODUCTION
Classifications of Spectroscopy
other with respect to the and again the resulting energylevel separa
field,
X
E = E cos2irv(tf)
4 INTRODUCTION TO MOLECULAR SPECTROSCOPY
"I W
Although, as will be seen later, the frequencies of the radiation that
are absorbed or emitted in a spectral study are more directly related to
the molecular energy changes that cause the absorption or emission, it is
Ae = hv (3)
INTRODUCTION 5
*\ (4)
erg/molecule cal/mole
PRINCIPAL REFERENCES
Experimental Methods
1. Harrison, G. R., R. C. Lord, and J. R. Loofbourow: "Practical Spectroscopy,"
PrenticeHall, Inc., Englewood Cliffs, N.J., 1948.
2. Gordy, W., W. V. Smith, and R. F. Trambarulo: "Microwave Spectroscopy,"
John Wiley & Sons, Inc., New York, 1953.
3. Sawyer, R. A.: "Experimental Spectroscopy," PrenticeHall, Inc., Englewood
Cliffs, N.J., 1944.
Applications
1. Bellamy, L. J.: "The Infrared Spectra of Complex Molecules," John Wiley &
Sons, Inc., New York, 1954.
2. Lawson, K. E.: "Infrared Absorption of Inorganic Substances," Reinhold
Publishing Corporation, New York, 1961.
3. Gillam, A. E., and E. S. Stern: "An Introduction to Electronic Absorption
Spectroscopy in Organic Chemistry," Edward Arnold & Co., London, 1954.
1 INTRODUCTION TO
THE THEORETICAL TREATMENT OF
MOLECULAR SYSTEMS
tions stems from Planck's studies of the radiation emitted by hot bodies.
He was 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
oscillation a proportionality constant, Planck's constant. Fur
and h is
energies emitted when an oscillator jumps from one of the allowed energy
levels to a lower one. The unit, or quantum, of energy given out in such
a jump from one energy state to the next lowest one is, therefore,
Ae = hv
The idea of discrete energies and the prominent role played by the
constant h were basic features of Planck's blackbody radiation deriva
tion. They seemed, however, to be awkward and troublesome features
since, in classical treatments, they could not be justified. Planck's
blackbody theory was, however, a preview of the developments in molec
ular theory and spectroscopy that were to take place in the next half
century. His reluctantly proposed ideas of quantum restrictions
were accepted and expanded into more elaborate theories of molecular
behavior, and his interpretation of the continuous spectrum provided by
a hot body was to be followed by analyses of spectra of great detail and
complexity.
In the next few years after 1900 the ideas of Planck were applied
and extended, as in Einstein's theories of the photoelectric effect and the
heat capacity of The next major step of spectroscopic interest
solids.
was the application of these ideas of quantum restrictions to atomic
systems, in particular to the hydrogen atom, by Niels Bohr in 1913.
where m is the mass of the electron, v its velocity, and r the radius of its
orbit. The requirement that the electron should have the coulombic
force of attraction to the nucleus balanced by the centrifugal force gives
t =
r2
^ r
(2)
or
(3)
mv 2
where e is the charge of the electron. Elimination of i>
2
, by means of the
quantum restriction of Eq. (1), gives the radii of the orbits in which,
according to Bohr, the electron is allowed to travel as
r — n' (4)
47r 2 me 2
Substitution of numerical values for the constants gives the radii of
the Bohr orbits as
8
The convenient unit of angstroms, defined so that 1 A = 10 cm, has
been introduced.
Of more interest in spectroscopy are the energies of the allowed
orbits. If the potential energy at infinite separation of the electron and
PE =   (6)
r
Addition of the kinetic energy gives, for the total energy of the electron,
the result
t = KE + PE
= mu2  (7)
g 7
Use can now be made of the relation of Eq. (3) and the quantum restric
where the fact that each value of n implies a value of e has been recog
nized by writing «„. This result gives, according to the Bohr theory, the
possible energies that the electron of the hydrogen atom can assume.
Elaborations of this result have been made to allow for elliptical
orbits, to take into account that the electron and nucleus should be
treated as rotating about the center of gravity, which is not quite at the
nucleus, and to include the relativistic dependence of electron mass on
velocity. These details need not, however, be treated here.
It is interesting to see that the condition that the angular momentum
be quantized in units of h/2K leads to a set of allowed energies. Further
more, if atom is now assumed to jump from
the electron of the hydrogen
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 (l!
be emitted. With the Planck relation Ae = hv, the Bohr theory leads to
the prediction of emission of radiation with frequencies
At 2ir
2
me*/l 1 \
'
=
T =
f^\n\ ~ </ Wlth ni
> W2 ^
In terms of the more often used units of cm 1 one , has the prediction
v 2w*me /l l
1\
cm
"c'ehrltf*) (10)
the case, the probability is given by ^V, where <j/* is the complex con
jugate of ^.)
INTRODUCTION TO THE THEORETICAL TREATMENT OF MOLECULAR SYSTEMS 13
fe
2
dy =
8ir 2
m da; +
2
U(x)+ e* (13)
(The first term can, in fact, be associated with the kinetic energy of the
particle, the second with the potential energy, and the sum, there
fore, with the total energy. It is perhaps better at first merely to
use the equation to calculate desired quantities much as one does with
/ = ma.)
Solution of a particular problem requires values of m and an expres
sion for the potential function to be substituted. The function ip that
solves the resulting differential equation must then be found. Such a
function will generally exist only for certain values of e, and these values
are the allowed energies of the system that are being sought. The square
of the solution function gives, as mentioned, the probability of the par
ticle being at various positions. The hydrogenatom problem would
require the value of m and the expression
for the electron to be used
—e 2
/r to be put in as the potential function. (The hydrogenatom prob
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
of \f/
an infinite probability of the particle being at a given position;
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 \[/
h2 dV
87r 2 m dx i 4 (14)
T .,
Lett side
.,
= — h2 ( nVj \ A 2
. .
sin
nirx
„ „
2
I
2
)
»7r OT V o / o
n 2h 2
8ma 2
Right side = c I A sin
J
(17)
s
The left and right sides of Eq. (14) are equal, and the expression
UTTX
^ = A sin
m3A J
n = 1,2, 3, (18)
8ma s
No really different solutions can be found, and no energies other than
these will result. [The value n = in Eq. (15) provides a solution to
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 there
fore unacceptable.] The allowed energies t, which are represented 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
similar situation occurs generally in atomic 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 functions for the particle in a box
problem.
e4 = 2
16(A /8 ma
2
)
t3 = 9(r/8ma)
£2 = 4<ft J /8ma*)
—
16 INTRODUCTION TO MOLECULAR SPECTROSCOPY
ii — A sin
o
^ = A* sin 2 — (19)
sufficient to have the solution functions and allowed energies stated with
out derivation.
As an illustration of this Schrodinger equation problem the one
dimensional squarewell, or "particleinabox," solution can be applied
to the question of the energies of the doublebonding or r electrons of a
conjugated system. 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
onedimensional region of uniform potential bounded by regions of
infinitely high potential. The allowed energies of the ir electrons, ignor
ing electronelectron repulsions, are then those given by the previous
derivation; i.e., « = n 2 2/8ma 2
/i . To apply this squarewell approxima
tion to the w electrons of a conjugated system, it remains to recall the
Pauli exclusion principle which requires that no two electrons of a mole
cule have quantum numbers the same. Since the spin of an
all their
if/* dx (20)
/:
For the particleinabox problem, since ^ is zero everywhere outside the
region to a, the limits can be reduced to give
/
"
r dx = 1 (21)
A*sm*—dx
a
= 1 (22)
/.o
The integration can be performed (or read from tables which give, if m is
an integer, / sin 2
my dy = t/2) to give
rin*^«fa = £ (23)
/oo o, Z
or
A =
^ (24)
= Sm (25)
^ Va "i"
+
/_ i*dr
." = 1 (26)
+
= 2? )
/_ „" ^** dT 1 <
17. Orthogonality
/+« Mm dr =
INTRODUCTION TO THE THEORETICAL TREATMENT OF MOLECULAR SYSTEMS 19
+ =
." +*+ dT (28)
/_
show that
JC
o
sin —
a
sin
a
ax = (^9)
of Eq. (29) to
"
/ sin ly sin my dy
and
sin my = ^. (e
imy  <r im ») (30)
ble to the wave functions for states with different energies. Some addi
tional features must be considered when there are several states, i.e.,
wave functions, corresponding to a single energy of the system.
A summary of this and the previous section can be given by the
statement that if 4> t and 4*m are normalized, real, wave functions cor
responding to nondegenerate states of a system
/+».,, I = for I a* m /o n
Fig. 11 that those with even values of n are functions that are antisym
metric about the midpoint of the well while those with odd values of n
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 done in the squarewell case, the solution functions are sines and
cosines as shown in Fig. 13. It is then possible to investigate the sym
metry properties wave functions by investigating what happens
of the
when y is replaced by —y
in a. particular wave function. When this is
done for the functions shown in Fig. 13, one sees mathematically that
FIG. 1 3 The symmetry properties of the partideinabox wove functions. (The wave
function! shown are not normalized.)
a/2 6 +«'2
—u +y •
INTRODUCTION TO THE THEORETICAL TREATMENT OF MOLECULAR SYSTEMS 21
For n odd
Hv) = Hy)
For n even (32)
My) = Mv)
Again one sees that for odd values of n the. function is an even, or sym
metric, function; while for even values of n the function is an odd, or
antisymmetric, function.
G+ = g+ (33)
* 87r
2
m (^Xt)'*
5
?
wVa sin
ir
=
w* (35)
: a
Sm = C° S
W« T) 2Vi VH \T) IT (36)
Variable Operator
Position
x x
v y
z z
Linear momentum:
h a
2jr» dx
h_d_
Pv
2vidy
h a
P.
2fridZ
Angular momentum:
M x —
h
VriVaz
/
\y
a
2 —a\ or
ay/
}
— —
2iri
h /
I
V
sin 6
a
ae
^
cot S cos d> —a\
34,/
I
M v
"
—h / a
\z
2xiV ax
x
a\
—
at)
J
or
— h
2irt\
/
I cos d>
a
ae
cot fl sin d> —a\
a<t>J
I
h / a a\
M ' X
2^A 7y V 7x)°
T
±/±)
2irt \a<t>/
r_i_ / l_
— a_ a\ aa 1
M« = M I + Ml + Ml j^_
2 v
".
m ae) a* 2 J
4t Lsin e ae sin* e
Kinetic energy:
h* ( i
a' a2 \
i^vl+vl+vl) ^Kw+W+6*)
Potential energy:
V{x,y,z) V(.x,y,z)
INTRODUCTION TO THE THEORETICAL TREATMENT OF MOLECULAR SYSTEMS 23
not a constant for one of the allowed states. Rather it has various
values at various positions. For such functions, the average value of the
variable is obtained according to the general rule
+"
f*G+dT
/ (37)
+
f_
y*idr
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)
mcx\ h nvx
P„ " = (nir\
f" (
U T
J2 . /2 ,
Sm C°S dX
jo W« IT) 2S V« )
nh fa nwx rmx
= i; 2
/
.
sin cos
,
ax
ia Jo a a
_ nh / a \ [" . j titxI"
ia? \2mr) _
a Jo
= (39)
many the n = 2 level; and so forth? (In Sec. 15 the tacit assumption
that the lowest available levels would be occupied was made.)
The answer to such questions is given by the Boltzmann distribution
which states that the number of particles N, occupying a state with
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 )
^! = e
(E E,)IRT
t
(41)
Ni = JVoe<«*»* r (42)
is here ignored.
The question that is asked is: What type of vibrational motion does
the particle of mass m undergo?
The answer clearly depends, among other things, on the nature of
the spring. It is found that many springs are such that if the particle is
FIG. 21 The absorption of radiation in the infrared spectral region by (a) a diatomic
molecule and (b) a polyatomic molecule. In general, the greater the number of atoms
in a molecule, the more ways the molecule can vibrate and the more complex is the
infrared absorption spectrum.
Wave numbers in cm 1
4,000 1,400 .1,200
5,0001 3,000 2,000 1,500 l,3O0  1,100 1,000 900 800 700 62
100
xV
I 1 1 1 1 1 1 1
<
80
60
40
20
COin CCI 4
n •
(a)
100
ft 7 8 9 10 16
Wavelength in microns
(b)
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 27
/ <* x (1)
or
f = — kx (2)
It is more convenient to deal with the force / that the spring exerts on the
particle and, since it is this force that the applied force acts against, one
has / = /.ppii.d and
dU = (/) dx
or (4)
dU _
J
dx
dU
j =
,
kx
dx
or (5)
dU = kxdx
If the equilibrium position is taken as that of zero potential energy,
integration of Eq. (5) gives
U = Px* (6)
the equilibrium position. If, as Fig. 226 indicates, the length of the spring
is I and the equilibrium length is I,, the previous results are expressed as
The equation describing the motion of the particle can now be set up.
One way of doing this is to substitute into Newton's / = ma equation to
obtain
d %x
— kx = mji or — kx = mx (8)
i(S).+£
One can note that, since
dT d (dT\
,. = mx and = mx
ax dt\Tx)
the same expression
mx + kx = or — kx = mx (11)
back into the differential equation. When this is done one obtains an
equality if
—4f7r 2 v 2 m = —k
or (14)
1 Ik
2t \m
30 INTRODUCTION TO MOLECULAR SPECTROSCOPY
tional energies will be allowed), but it will be seen that the quantum
mechanical solution retains a considerable similarity to Eq. (14).
for simplicity, be allowed to move only along the line of the system.
Again it is asked What : is the nature of the motion that these particles
undergo?
FIG. 23 The shape of the potential energybond length curve for a diatomic molecule.
The displacement coordinate q is defined as q = r  r,.
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 31
T = %{m\x\ + wi2X?)
"
and (15)
U = \k(x,  Xl y
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. For each particle i, one writes the Lagrange
equation as
d/dT\,dU . ,,,..
and (18)
Xi = A2 COS (2irvt + <p)
tional solution is to be found, the frequency will be that of the system and
must be the same for particles 1 and 2. Substitution of
£1 = — 4x 2
i'
2
Ai cos (2irvt + </>)
and (19)
Xz = — 4jr 2
v 2 A.2 COS {2wvt + <p)
One can now eliminate Ay or A 2 from these two equations to get a relation
for v. This is most conveniently done by recalling that for such linear
homogeneous equations nontrivial solutions for the A's will exist only if the
determinant of the coefficients of the A's is zero. That is,
(47rVmi + k) k
(21)
—k ( — 4jr 2
p
2
m +
2 k)
v = (23)
and
2~ \/~ where = ^
mi + ^
n _^_ (24)
2t \h wi2
Ai = A 2 (25)
A, my
and (26)
Xi TO 2
=
Xi my
If the two masses are equal, one gets Ay = — At. and xi = — z2 . The
motion corresponding to v = 1/2* s/k/y. can be generated, in view of
Eqs. (18), by displacing the particles from their equilibrium position by
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 33
equal and opposite amounts. The motion that will occur will clearly be
one of vibration and have the frequency v = 1/2t s/k/ii.
will
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 ,
Exercise 21. Obtain the relation between A and A 2 for the two roots
x
Q.
— Xi — Xl
(27)
X = m&i + mzXz
mi + m 2
Xi = A j
q
and (29)
Xi = A + mi + m *
2
i
q + kq =
or (31)
nq + kq =
This can be recognized as identical to Eq. (11) for the vibration of a single
particle. Only a change in notation from m to n and x to q has occurred.
The solution to Eq. (31) is, therefore, the same as that for Eq. (11), and
we can write down the solution as
and
(mi + mi)X =
or (34)
X=
A solution which is formally like that obtained previously is
Exercise 22. By finding the inverse of the transformation matrix for the
x's in terms of q and X, obtain the expressions of Eq. (29).
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 bond
of the molecule from its equilibrium distance.
Except for the case of H 2 , it has not been possible to calculate the
energy of the molecule as a function of internuclear distance from the
interactions between the bonding electrons and the atomic nuclei. The
general shape of the potentialenergy versus bondlength curve can, how
ever, be sketched. One knows, for example, that if a bond is stretched
far enough it will break, i.e., a molecule can be dissociated, and that bonds
strongly resist compression, as is by the relative
revealed, for example,
incompressibility of solids. and more exact ones
Such qualitative ideas,
yields curves of the shape of that in Fig. 23 has been given by P. M.
Morse. He has suggested the relation
where, as before, q measures the distortion of the bond from its equi
• librium length; D e is the dissociation energy measured from the equi
librium position, i.e., from the minimum of the curve; and /3 is a constant
for any given molecule and can be said to determine the narrowness, or
curvature, of the potential well. The Morse curve with the values of
D e and j3 that are appropriate to HC1 is shown in Fig. 24.
Exercise 23. The value of /? in the Morse equation can be conveniently
calculated from the relation
0_, W^
for H 2 for which <b e = 4,395 cm and D e = 38,310 cm
1 1
Determine .
= (dU\ 1 /dHJ\
U(q) !7_, + \dq),<>
9 + 2\dq*) Q= „
q* + (36)
FIG. 24 The harmonic oscillator (dashed line) and Morse (solid line) potentialenergy
functions for HO.
40,000
i
30,000
E
u
c
i«
e
3 20,000
10.000
V= 134,000(p  re y\
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 37
while that for the vibrations of a diatomic molecule with reduced mass
ju is, correspondingly,
?& + (I *A+*
^
= ^ fcQ;2 (39)
8* 2n dq 2 V2 )
(' + where v = 0, 1, 2,
5)s> (40)
These allowed energies are shown, along with the potentialenergy func
tion, in Fig. 25. The appearance in Eq. (40) of the same quantities as
in the classical calculation of a vibrating system should be noted. This
p =3
i> =2
v =l
«.(» + i)fo* ( 41 )
where w = 1/2t y/k/p is written for the frequency with which, according
to Eq. (14), the system would vibrate if it behaved classically. (In
what follows, to will be used for a molecular vibrational property and v
will be reserved for the frequency of radiation.)
The form of the solution functions, or eigenfunctions, is also shown
in Fig. 25. Although little will be done with the solution wave func
tions 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
(42)
4> v = N el°<>'H
v v (V*q) where v = 0, 1, 2, . . . (43)
^ = (^^\
V2V.VV
"
(44)
For most purposes it will be enough to recognize the form of the solution
functions shown in Fig. 25. For those unfamiliar with the Hermite
polynomials it may be informative, however, to write down a few of the
first solution functions.
*o = 1
~ e iaq'
(i)'
ft = V 2a("V
/
qeM
K;)'
!
4>i = y=
(Y
(2a?2 ~ 1)e_i "' (45)
= ~ iaq '
**
Vi (»)*
{2aiq3 ~ Zaiq)e
(f\'
A« = ^,«. = A^ (46)
can occur with the absorption or emission of radiation and what energy
levels are appreciably populated at the 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 men
tioned here. First of all, it will be shown that a vibrating molecule
cannot interact with electromagnetic radiation unless a vibrating, or
oscillating, dipole moment accompanies the molecular vibration. Qua
litatively, one can picture an oscillating dipole as coupling with the
electric field of the radiation so that energy can be exchanged between the
molecule and the radiation. 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 lengths, will fail to interact with radiation and will exhibit no
vibrational spectral transitions. On the other hand, a heteronuclear
diatomic molecule will generally have a dipole moment and, generally,
the dipole moment will be dependent on the internuclear distance.
The vibration of a heteronuclear diatomic molecule will, therefore, be
generally accompanied by an oscillating dipole moment. Such molecules
can interact with radiation and can absorb energy of the radiation and
can thereby change their vibrational state to one of higher energy.
They can, also, emit radiation energy and thereby change their vibra
tional state to one of lower energy.
One further transition restriction, which will be discussed in Chap.
4, must be mentioned. Even for those molecules that have an oscillating
dipole moment there is the further restriction, which is rigorously applica
ble only to harmonic oscillator type systems, that the vibrational
quantum number can change only by one unit. Transitions are allowed,
therefore, only if
Av = ±1 (47)
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 41
= 0.008 (48)
Thus, less than 1 per cent of the molecules are in the v = 1 state, and
negligibly small numbers will be in still higher energy states. It follows
v = 3 X 10 10
(2,890) = 8.67 X 10 13
cycles/sec
Ae = hv = 6.62 X 10"(8.67 X 10 13 )
= 5.74 X 10 13 erg . (49)
h lie
Ae = (50)
Mhci
We + Wei
= 1.627 X 10 24 g
42 INTRODUCTION TO MOLECULAR SPECTROSCOPY
one obtains
H 2 4,159.2 5.2 X 10 5
D 2 2,990.3 5.3
HF 3,958.4 8.8
HC1 2,885.6 4.8
HBr 2,559.3 3.8
HI 2,230.0 2.9
CO 2,143.3 18.7
NO 1,876.0 15.5
F, 892 4.5
CI* 556.9 3.2
Br* 321 2.4
I* 213.4 1.7
o. 1,556.3 11.4
N a 2,330.7 22.6
lis 246.3 1.3
Nas 157.8 1.7
NaCl 378 1.2
KC1 278 .8
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 43
This expression for the potential can be used in the Schrodinger equation
to deduce the energy levels of the allowed states of the anharmonic
oscillator. The solution is obtained by an approximation, or perturba
tion, method and leads to an energylevel expression that can be written
as
«. = «.(» + *)  ^J. (v + i) J
(56)
44 INTRODUCTION TO MOLECULAR SPECTROSCOPY
Here o> e has been written for convenience in place of 1/2tc y/k,/\i where
fc 8 = (d 2 U/dq 2 ) q „o. This quantity w e is, therefore, the spacing of the
energy levels, expressed in cm1 , that would occur
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
quantumnumber term is known as the anharmonicity constant. It is
always much
than the principal term £> e
less With the minus sign .
FIG. 26 The vibrational energy levels calculated for HCI. Pattern (a) is based on the
harmonicoscillator approximation and the frequency of the fundamental transition.
14,000
12,000
10,000
<
8,000
B
£ 6,000
4,000 
2,000
Harmonic Anharmonic
(a) (b)
THE VIBRATIONAL ENERGIES OF A DIATOMIC MOLECULE 45
vibrating particles less closely than would a parabolic curve. Such loosen
ing of the restrictions on the motion of particles always leads to more
closely spaced allowed energy levels. The anharmonicity term intro
duces, therefore, an effect which decreases the spacing of the higher energy
levels, as shown in Fig, 26.
If one observes some of the overtone bands, i.e., transitions from
One finds, for a>„ = 2,988.90 cm1 and u^x e = 51.60 cm1 , that Eq. (57)
provides a very satisfactory fit to the observed frequencies of HC1.
One notices that «„ is considerably larger than the quantity «(1) —
i(0) 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.
The distinction is that &>« is a measure of the curvature of the potential
curve at the very bottom of the curve, where a hypothetical v = — ^ level
would be. The harmonicoscillator approximation takes the difference in
energy of the v = and =
1 levels as a measure of the curvature
v of the
potential curve and therefore gets a lower value. Thus for HC1
Soto cm *
Harmonic Anharmonic
oscillator oscillator
while
PRINCIPAL REFERENCE
In the previous chapter it has been shown that changes in the vibrational
energy of simple molecules can lead to absorption, or emission, of radia
tion in the infrared spectral region and that information on the frequency
of the radiation absorbed, or emitted, can be used to determine the stiff
ness of the bond holding the atoms together. It is now natural to ask
whether the rotational energy of a molecule is also quantized, whether
changes in the rotational energy can lead to the absorption, or emission,
of radiation, and, if so, what molecular property can be deduced from a
study of the frequencies of radiation emitted or absorbed.
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 of the examples of linear
molecules, the theory that is developed is equally applicable to linear
polyatomic molecules. It is again convenient to consider first the
classical behavior of a linear mass system and then to see the difference
in behavior that is imposed when the system is of molecular dimensions
and the quantum restrictions become important.
No attempt will be made in this introductory treatment to allow
for the fact that the molecules undergo simultaneous rotation and
vibration. The rotational effects will be considered by themselves. A
treatment that assumes that the molecular dimensions are independent
of molecular vibrations and undisturbed by molecular rotation is known
as the rigidrotor approximation. A final section will consider the slight
47
48 INTRODUCTION TO MOLECULAR SPECTROSCOPY
= 2
'(^H (i)
It follows also that the number of revolutions per unit time, i.e., the dis
tance traveled per unit time divided by the circumference of the particle
path, is v/2vr or <a/2v.
The moment of inertia of a system is defined as
I = Y,
mr' i
(2)
where n is the distance of the ith particle from the center of gravity of
the system. For any particular system, the value of / can be worked
out by first and then applying Eq. (2).
locating the center of gravity
For a diatomic molecule, for instance, the masses and distances of
Fig. 31 lead to the center of gravity being located so that
C.G. mi
THE ROTATIONAL ENERGIES OF LINEAR MOLECULES 49
+r =
or, since r x 2 r, to the relations
m
n = mi + m r
2
:
and (3)
mi
r2 = r
mi +r
wi2
Application of the denning equation, Eq. (2), for the moment of inertia
now gives
. _
(nil
mfm 2
+m 2)
2
2
.
(m t
m y m\
main\
+m
—
2)
2
r2
= mim 2 ,
r2
+m
j
mi 2
= iur
2
(4)
wtim 2
m  m7 +^r2 («)
=  £ m,coV? =
t
WX i
"W?
= i/" 2
(6)
Exercise 31. Calculate the moment of inertia of (a) HC1 85 HC1 87 and
, ,
DC1 36 ,
all of which have an equilibrium bond length of 1.275 A, and (b)
N 0, which
2 is linear and has N—N and N— bond lengths of 1.126 and
1.191 A, respectively.
50 INTRODUCTION TO MOLECULAR SPECTROSCOPY
J) (rnivdu
i
'Si* (9)
ej = ^jJ(J + D (10)
rather than by the simpler form J(h/2w) introduced by Bohr and used
lj = BJ(J + 1) cm 1
(13)
FIG. 33 The energylevel pattern for a rotating linear molecule. The degeneracy, or
multiplicity, of each rotational level is indicated by the number of levels that would appear
if an electric field were applied to the rotating molecule.
Energy pattern if
Allowed 2/ +
I degeneracy
rotational were removed
«,= J&/t7 + 1J energies (schematic) Multiplicity
30E U
20B
12JJ
6B
2B
OB
THE ROTATIONAL ENERGIES OF LINEAR MOLECULES 53
AV^o
10 15 20 25 30 35 40 45
Rotational quantum number, J
54 INTRODUCTION TO MOLECULAR SPECTROSCOPY
The result of this example, that quite a few of the allowed rotational
energy levels are appreciably populated, is generally valid. It follows
AJ = ±1 (16)
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, is
= 2B(J + 1) ( 17 >
THE ROTATIONAL ENERGIES OF LINEAR MOLECULES 55
FIG. 35 Rotational energy levels and transitions for a rig id rotor linear molecule.
The symbol B is used to represent the quantity h/87T 5Jc.
Energy
— 30B
Ai=105
Spectrum
56 INTRODUCTION TO MOLECULAR SPECTROSCOPY
From these data one can obtain an average value of the absorption
line spacing of 12,162.7 megacycles/sec and
S =
12 16
2( 2 9 9 790
7
X Z) = ° 20285 ^ (18)
Therefore, since B = h/STr 2 Ic, the moment of inertia of the OCS mole
cule can be calculated to be
5 i 6c i2 S 34 = 0.197910 cm 1
and 7 0l6c i 2s 34 = 141.4 X lO" 40 g/sq cm
From these momentofinertia data, and the assumption that the bond
lengths are independent of the isotopic species, one deduces that in the
OCS molecule
16
TABLE 31 Absorptions of C 12 S 32 in
Transitions*
Transition Frequency v
J — J +
> 1 (megacycles/ sec)
0» 1
l>2 24,325.92
2* 3 36,488.82
3>4 48,651.64
4>5 60,814.08
* From Strandberg, Wentink, and
Kyhl, Phys. Rev., 75: 270 (1949).
a
H
c
led to very accurate values for the moments of inertia and, in many
cases, for the lengths of the bonds of molecules. Some of these results are
shown in Table 32.
Close examination of data such as those of Table 31 reveals that the
spacing between adjacent spectral lines is not, in fact, exactly constant.
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 cen
CO C=0 1 1282
.
r = _Jr° (23)
k — rrua*
t =
2
Iu> + 2~¥~
= I
2
7o)2 + I(W
2 fcr
2
(25)
= ^^ + 1) + 32^^ +
It is finally necessary to relate the distorted distance r in the first term,
1)2 (26)
tj =
"2
^D
'(' +
gSSFT^ '
.J^'V +
3ar*mVJIb
l)' (27)

D = 4B>/tf (30)
The value of D is always very muchthan that of B, and the
less
difference between the rigid and nonrigid rotor treatments can, as Fig. 36
J
8 —
ft
5
involved.
The expression for the energies of the rotational transitions AJ = +1
for a nonrigid rotor are, according to Eq. (29),
distortion.
PRINCIPAL REFERENCES
_ v a*9(z,t)
U(xn(xt) _ _ j_g*M m
61
« INTRODUCTION TO MOLECULAR SPECTROSCOPY
Previously it was shown that 4/*^ described the system, i.e., gave
information on the position of the particle, in the onedimensional square
well potential. In a similar way, *** describes the system in space
and time.
To reduce equations such as the timedependent Schrodinger equa
tion to more manageable forms, it is customary to try to separate them
into two equations each involving only one of the variables. With this
approach one tries the general substitution
&*&*> + "»«**«>&*(*!&
or (3)
h 1 d*(<)
2
m dx 2 J
dx*
+
^ 17(35)
v
'
= 
2ti dt
<Kx)
'(x) [
L 8ir <*>({)
The left side of this equation is a function only of x, and the right
side is a function only of t. The equation can be valid for aH values of
x and t, only if each side is equal to a constant. The constant is called e
since it can be identified with the energy of the system. The two
equations that are obtained by setting Eq. (3) equal to the constant * are
4jja «*«, (*
and
A 2 dV
&w 1mdx i
+ U(x)f = e+ (5)
ent part of the complete Schrodinger equation can be readily solved, and
the solution is
where «„ is written because the values of € that are required by Eq. (5)
involve a quantum number which can be denoted by n. The solution
THE ABSORPTION AND EMISSION OF RADIATION 63
where
nn
(8)
8ma 2
The implications of the solution in x and t can be seen if the quantum
mechanical description of the system, as given by **'4 is obtained. r
,
= *V (9)
The timedependent part of the solution to the space and time equa
tion is seen, therefore, to drop out, and the system is again described
simply in terms of the timeindependent wave functions. Systems, like
the particleinabox system studied in Chap. 1, which lead to solutions
that are time independent, are said to have allowed stationary states.
These are the allowed states that are obtained as solutions to the time
independent Schrodinger equation.
For a spectroscopic process to occur, a procedure must exist which
causes a state to change from one stationary state to another. How a
time dependence is introduced into a quantummechanical problem will
now be investigated.
assumed to have only a lower energy state, with a wave function \[/i,
and an upper energy state, with a wave function m where I and m are \f/ ,
h* d2
8w 2m dx 2
+ ,
TT
U(x),
,
and (12)
* = a&i + am ^r m (13)
but, as we will see, can be functions of time. The two allowed stationary
states of the system are described by the general expression with Oj = 1,
am = or a t
= 0, am = 1.
H '£a£' + ™ (14)
The Schrodinger equation for this initial, unperturbed case is then written
as
ff (15)
"*aSS
It is this equation that has the two solutions fy and ty m .
am
2« " dt 2wi
l
dt 2ri ~dT {
'
+
The first two and last two terms cancel because ¥j and Wm are solutions
of the unperturbed wave equation. The remaining expression is simpli
fied if it is multiplied through by V* and integrated over all space, i.e.,
from x=— «>tox— +00. 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"» ?« fljer< f 
dt h
, H/A) ( „_« m) ,
^H h dx
,
2m /"+«
~ h
e f, idx (19)
dt h
It is here more convenient to use the exponential form for the time
THE ABSORPTION AND EMISSION OF RADIATION
energy of the system and is responsible for the change in that occurs H
when radiation falls on the system. One can write, therefore,
+"
^2 =
(£t
~E° f— tltx^i da;(e< 2
* i "'>«»«'+A'><
+ e (*r«/« «„.,«<)
th
J 00
(24)
The process of interest here is that in which the system goes from a
lower energy level u to a higher one e m For such an arrangement of .
hv = t m  e,
•
(27)
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
,
ence would lead to a zero denominator. It follows that the first term
in the square brackets is important if the transition from I to m isone
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). We have, therefore, for
the assumed energylevel pattern
[1
_ t>iirilh)ii m —T\,)t~]
described by the product ¥*&, where * = a&i + am ^rm and the a's are
time dependent. This quantummechanical description can be given
as a function of time if it is integrated over all values of x. This integra
tion, moreover, removes all the spacedependent wave functions because
of their orthogonality and normalization. One is left only with
/_«" *** dX = a l
ai + am a ™ ( 29 )
— 1—
al{t)a m {t) = mm HEIY  ,
L (e m — ei hvy 
The above
rrtwi
expression shows the effect of a given frequency of radiation.
(3o >
+" sin 2 x
—5— ax ,
/:
the result
a*
m {t)a m (t) = ~ \ii* m \KK)H (31)
P = ^ (KY (32)
where p is the energy density, i.e., the energy per unit volume that is
— Jt w *ft. p (33)
J t
(o£Om) = jj£j
\(Hxlm)
2
+ {HylmY + G*»lm)*p
= % wV (34)
= B lmP (35)
J (OrnOm)
t
with
3
8ir
B tm = gp Wm 2  
(36)
sin 2 (2ir/h) (e m — —
«; hv)
(«». — «i — hvY
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
the intensity of the radiation after passing through the cell containing
the solution. The integrated form of Beer's law is obtained in this way
as
aOOijln^ (38)
ir dl
a(v) dv
/.over band
or (39)
A = [ a(v) dv
J over band
= A
c
dl = p Wm V^JV'  
dl (41)
I = cp (42)
dl = §£ Wm 2 ()  
hv lmN' dl (43)
N' = NC (44)
v ;
1,000
72 INTRODUCTION TO MOLECULAR SPECTROSCOPY
 d7
Sw@^S a (45)
2
yjmlWml (46)
3/ic(l,000)
+
iMtml = /_ „T **"* dx ( 47 )
+ /xim and thereby learn, by means of Eq. (47),. something about the
wave functions of the states involved in the transition. In subsequent
work, both procedures will be used.
ft = ey (48)
where, as Fig. 42 shows, y is the distance of the electron from the center
of the potential well. For a transition from a state with » = ItO one
with n = m to be induced by electromagnetic radiation, the integral
must he nonzero.
The integration will be carried out in the next section when a
quantitative result for the absorption intensities is desired.' One can
here illustrate that for the deduction of selection rules it is often sufficient
to consider the symmetry of the three functions if/*, ey, and that appear^
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 anti
symmetric, function since it changes sign at the origin. All the wave
— (odd function)
~ ea
/»
= •1{' ~ = ex (50)
I) 2
. nwx
*„ =
1
sin (51)
\ja a
THE ABSORPTION AND EMISSION OF RADIATION 75
, ,
2e
I
Mi*
one gets
ImiI
=  l"
a Jo
\
x cos (I  m)—
a
 x cos (l + m) — \dx (55)
I "J
Integration, making use of the integral (y cos y dy = cos y + y sin y,
gives
where the fact that I — m and + m I are integers has been used to elim
inate the sine terms.
The selection rules deduced from symmetry considerations in the
previous section can be obtained analytically by the insertion into
Eq. (56) of the various even and odd combinations for I and m.
The intensity of the ireleetron transition of hexatriene, for which
the frequency was calculated in Exercise 12, can be used as a specific
. .
_ 96 ea ^ 2ea (
~~
8**N 4e 2 a 2
3Ac(l,000) "" **
_ 32NeWvlm (58)
SwhclflOO
in Sec. 43, that the term for induced emission is equal to that for induced
absorption. This means that, if there are the same number of molecules
in the state to as in the state I, the effect of subjecting the system to
electromagnetic radiation will be to cause just as many molecules to go
from m to from I to to. No net absorption of energy will be observed.
I as
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.
In addition to induced absorption and emission, there is the possi
bility of spontaneous emission. The probability of such emission is
usually much less than for the induced process, and it need not be treated
here.
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 ,
(y) dv
l A Jo°
dv see
1
cm1 mole1 liter
A 
31^0) vM * SeC_1 Cm_1 m°le_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 ,
.
1
3Rlfj0) ^W «« nudcr^ liter (59)
For the fundamental transition for which the values of the vibrational
quantum number v are I = 0. and m= 1, the expression for A is
where Mr*, is, essentially, the quantity usually referred to as the perma
nent dipole moment.
In terms of th.e displacement coordinate
q = rr, (62)
78 INTRODUCTION TO MOLECULAR SPECTROSCOPY
"='" + 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
*°
=
w e
~ aqm
and
where
and /i„ d .
is written to distinguish the reduced mass from the dipole
moment it.
can be set up, if only the first two terms of Eq. (63) are retained, as
+
IMoi 
=
/_
>[^o + (g) g]^ 9=o
(64)
+
M= (l) o/ 0#ldg 9
." *
=
(iL v^@7r^ ^
aa!
(65)
One obtains

Wl = 
_i=(£) (67)
THE ABSORPTION AND EMISSION OF RADIATION 79
and with this value for the transition moment the integrated absorption
coefficient A is found to be related to molecular properties according to
in£S^(%l
V «A=» 3c 2 (l,000)Mred. d
m
or
/djA _ /
3c 2 (l,000)Mred.A (69)
\dq) q,o ~ * \ *N
Equation (68) is the important result that shows how the absorption
intensity of a fundamental vibrational transition is related to the proper
ties M™a. and (dii/dq) q=a of the molecule under study. The transposition
given in Eq. (69) is that which is used when it is desired to obtain the
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
,
From this value and the reduced mass of 4.1 X 102 * g, one calculates
\dg/«=o
76 X 10 10 esu (71)
M = (Se)r (72)
and, since g = r — r„
~ ~
\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 is consistent with this expectation.
It is, attempt to express the dipole
in fact, rather unsatisfactory to
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
80 INTRODUCTION TO MOLECULAR SPECTROSCOPY
zero and that at r = °o, since in inert solvents or gaseous media essen
tially all bonds are expected to break to give neutral 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
sign of this equilibrium dipole moment. The information available,
including a deduced value of + {dn/dq) q=a from the measured value
of A,
can be illustrated by the curves for possible dipolemoment versus bond
distance 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 meas
urement of 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
siderable potential value in consideration of the electronic structure of
molecules.
molecule or ion.
One assumes that the electron that is responsible for the absorption
of the radiation is attracted to the center of the molecule, here assumed
to be spherical, with a Hooke's law type of force. With this model, the
FIG. 43 Types of ft versus r curves that can be drawn from measured values of fi and
dn/dq.
Mobs.
g — 0— +9
THE ABSORPTION AND EMISSION OF RADIATION 81
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,
according to Eq. (67) and the expression for a,
,. 3e 2 ft
Moi' (75)
8ir 2 TOvC
A = tt^f.
1,000cm
—
iVe 2
sec
1
cm1 mole1 liter
or (76)
Ne 2 2 1
A = * n„ n , cm , mole liter
l,000c 2 wi
,
= Ua(v) di>U,
3
[iVe 2 /l,000c 2 m]
= 4.33 X 10 9 /a(i;) dv (78)
PRINCIPAL REFERENCES
Some of the principal features of the energy levels of the allowed rota
tional states of diatomic molecules and of the transitions between these
states have been discussed in Chap. 3. The rotational energiesand
rotational spectra of general polyatomic molecules are conveniently
treated under headings that specify the relative value of the three
principal moments of inertia of the molecule. On this basis, the chapter
is divided into the three principal topics: linear, symmetrictop, and
asymmetrictop molecules. A number of aspects of the rotational spectra
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
C
o
V
>
"5
=
o
o
B
e
a.
a
S
E
o
i5
o HI
r "l".
85
86 INTRODUCTION TO MOLECULAR SPECTROSCOPY
satisfy the Schrodinger equation only if « in that equation has the values
8wU
J(J + 1) / = 0, 1, 2, . . . (1)
This result is the same as that obtained previously from the quantized
angular momentum restriction. Furthermore, if quantummechanical
operators for angular momentum given in Table 11 are used to compute
average angular momenta from the wave functions given in Table 51,
it is found that
h
Total angular momentum = \/J(J + 1) ~
TABLE 51 Some of the Wave Functions for a Rigid Rotating Linear
Molecule
1
J =0 Af =0 <P 7=
2Vi
/ = 1 M = ,=i^COS9
Af = +1 * =
1/3. 8mee OT
2\l%r
/i 5 .
1  .. / sin 9 sm *
J  2 M = ^ = «./
4 \ir
(3 cos
2
91)
M  ±1 i, — sin
= 1 A (16 .
9 cos 96*'* or
2 \2x
/ 1 /l5
\  .. / — sin 9 cos 9cos
. „
<t>
/1 5
1
\
1
1 
2
.. /
\
— sm
IT
• „
9 cos 9 sin
„ • ..
*
Af = ±2 &, =  »
4 \2ir
/ — sin 2
9e ±2i+ or
/ 1 /l5
I
)

4
../
\
— sin
IT
2
9 cos 2*
,
/ 1 (15
I «/— sin 2
9 sin 2c>
\ 4 \ jr
ROTATIONAL SPECTRA 87
where
M= 0, +1, ±2, ±J
The first of these is the now familiar total angular momentum stipulation,
while the second corresponds to the stipulation that the angular momen
tum component in a direction in space be quantized.
sometimes convenient to illustrate the angular momentum
It is
components implied by the rotational wave functions by means of
a vector diagram. The diagrams that result for quantization in terms
of \/J(J M
+ 1) and are illustrated in Fig. 52. The number of angu
lar 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.
Exercise 51. Apply the operator for total angular momentum to the
J = and +1 wave functions, and confirm that the average angular
momentum is y/J(J + l)(h/2ir) in these cases.
After the wave functions of the states involved are specified, the
remaining term that is necessary for the evaluation of the transition
moment integral is the dipole moment. If the permanent dipole moment
of the molecule is represented by /* , the components along the three axes
FIG. 52 The total and component angular momentum vectors for J = 2. For 1 = 1
an applied field reveals five components. More generally for the Jth rotational level
2) + 1 states would be revealed.
Angular momentum
component in direction
. of appl ied field
Angular momentum of
rotating molecule
KA/27T)
 2(ft/2T)
'
2
M
J'Jf'J"M" = MQ
f ' ^J'M' gj n fl CQS ^J'M" gm (20 df

[J
^j'Mjjf'i = Mo
o Jj
2
'
fw sin 8 sin W"*" sin dfl d« (4)
2x
J'*<j"<jf" = j" ' ^/'Af cos 0^j"K" sin de
 M Mo j" dtf)
o o
(It will be recalled that the element of solid angle is sin 6 dd d<t> in polar
coordinates.) These components allow the calculation of the total
transition moment as
It is immediately clear from Eq. (4) that the transition moment for
rotational transitions will be zero unless mo has a nonzero value. It
requires a more detailed investigation of the integrals to see that they
also vanish unless
J' J"±l
that is,
A/ = +1 (6)
Exercise 52. Deduce from the symmetry of the wave functions of Fig.
51and the antisymmetric nature of the dipole moment, as can be verified
from Eq. (3), that the transition moment for J = to J = 1 will be
nonzero while that for the J = to J = 2 will be necessarily zero.
ROTATIONAL SPECTRA 89
AM = (7)
Again, since the general proof of this requires a knowledge of the behavior
of spherical harmonics, it will not be given. One can, however, verify
that this selection rule operates for transitions between states described
by the wave functions of Table 51.
shifts that the states with given J and various values of M experience is,
however, not simply done. The effect of the applied field is, as will be
seen, very small, and the calculation of the energy requires a secondorder
perturbation calculation to be made. The derivation of the expression
for the energy shifts is beyond the scope of this treatment and is outlined,
with references, in ref . 2.
Se, where
for / ?*
5£ = "
«00P er &
These energy shifts in ergs can be converted to frequency shifts of
rules
AJ = ±1 AM = (9)
AJ = +1, AM = (10)
molecules that a simple matching of the spectral lines with the expected
pattern is seldom possible.
In addition to illustrating the space quantization effect, measurement
of Stark effect splittings allow, with the aid of Eq. (8), the determination
of often rather precise values of the molecular dipole moment /x The .
FIG. 53 The effect of a Stark field of 1.00Q volts/cm on the rotational energy levels
of HCI.
200 6X 10 6
y =4
150
M
0 4X10 6
±1
/ = 3  +2
±3
100
E
u
e
M E
§
2X 10°
^^^^ ±2
so
^ M = ±l
J = .
50 M=
No applied field 1,000 volts/cm 2X 10
6
92 INTRODUCTION TO MOLECULAR SPECTROSCOPY
D. K. Coles [Phys. Rev., 70: 560 (1946)] for the molecule OCS. The
oscilloscope pattern of the J = 1 to J = 2 line is shown for different
of Rotational Transitions*
ROTATIONAL SPECTRA 93
Vl(I + 1) where I = 0, %, 1, f
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, on the other hand, there 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
can be expressed by introducing a quantum number for the total angular
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 molecu
FIG. 54 The Stark splitting of the J = 1 * 2 absorption line of OCS. [From T. W.
Dakin, W. E Good, and D. K. Cotes, Phys. Rev., 70: 560 (1946).] The line for no field
iscentered 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 INTRODUCTION TO MOLECULAR SPECTROSCOPY
lar rotation state with a given value of J can then lead to states with
various values of F according to
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 J levels that result
acting on the nucleus that is now important. " Although s orbits, bring
their electrons close to the nucleus, they are ineffective in orienting the
nucleus because of their spherical symmetry. The next most effective
FIG. 55 The hyperflne splittings (schematic) of rotational levels resulting from coupling
with a nuclear spin / = s.
F
J — 9/2
3 —^h^^h 7/2
5/2
3/2
7/2
5/2
3/2
1/2
1
ROTATIONAL SPECTRA 95
for a given nucleus with a given quadrupole moment, with the extent to
which the p subshell of the atom is more or less complete in a particular
molecule [2].
AJ = + 1 AF = 0, + (12)
N 14
The energy levels and J = —> 1 transition,
has a spin of unity.
observed by Simmons, Anderson, and Gordy [Phys. Rev., 77 77 (1950) :

Frequency
F=
y= i
FIG. 56 The J = > 1 ab F=2
sorption and transitions for DCN F= l
/=0 F=l
)
It has been shown, in Sec. 18, that the wave functions for. the very
simple system of a particle in a box were either unchanged or changed in
sign when the wave function was subjected to an inversion through
the origin, i.e., when y was replaced by — y. On the basis of this behav
ior, the allowed states were labeled with a plus or a minus, depending on
their behavior with regard to this symmetry operation. It was found,
furthermore, that the selection rules (+ <— > — +
, <—I—> +, — «+> —
for the transitions induced by electromagnetic radiation could be deduced
on the basis of the plus or minus character of the states involved in the
transition. We will now see that plus and minus signs can, in an entirely
analogous manner, be assigned to the wave functions that describe
diatomic molecules. This positive and negative character is important
in connection with selection rules and with the statistical weights of
rotational levels, considered in the following section.
We now consider the effect on the total wave function ^t,! of a
diatomic molecule when this function is inverted through the origin, i.e.,
does not alter ^„. The second step reflects the electronic 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
molecule. 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
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 are of this type. Most groundstate wave functions, in
fact, are designed as 2+ states. The basis for the use of the letter 2
will be discussed in Chap. 10. For these often encountered 2+ states,
therefore, we conclude that an inversion of <p e through the origin leaves
\f> e
unchanged.
The vibrational component v of the total wave function, depends,
\j/
FIG. 57 Illustration that rotation by 180 deg around an axis and reflection through a
plane perpendicular to the axis correspond to inversion through the origin.
After rotation •
for the molecules considered here, one deduces that ^ to tai behaves in a
manner dictated by fn as shown in Fig. 58.
An immediate result of this assignment is the selectionrule result
(+ i > — +
,
<(—> +, — (  > — ) that can be deduced for interaction
with electromagnetic radiation in the same way as illustrated for the
onedimensional example in Sec. 45. This result can be recognized to be
consistent with that of A J = +1 obtained from a more detailed analysis
of the rotational wave functions.
We now will proceed to another important type of symmetry
consideration and will make use of the plus and minus assignments
obtained above.
Behavior of ^, otill
on inversion
helium atom may clarify the parallel treatment that will be given for like
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)
Each electron has a spin quantum number £, and since the angular
momentum associated with this spin can be directed one way, designated
say by the symbol a, or the other way, designated by the symbol p, one
can write various possible spin functions for \f>^ n as
«(1)«(2)
0(1)0(2)
a(l)j8(2) + a(2)/J(l)
a(l)0(2)  a(2)/S(l)
These have all been written so that f, Bin will go to +^, pi„ when the
electrons are interchanged.
To attach correct spin functions, from these four possibilities, to the
orbital functions, one must make use of the fact that the behavior of
electrons in nature can be accounted for only if wave functions that are
antisymmetric with respect to the exchange of any pair of electrons are
used. It follows that a suitable antisymmetric ^toui can be written by
combining the orbital and spin factors to give
One deduces by this means the familiar result, given immediately by the
100 INTRODUCTION TO MOLECULAR SPECTROSCOPY
usual form of the Pauli exclusion principle, that the electrons of the
helium atom, in its ground state, must have opposite spins.
In a similar way the total wave function for a molecule must behave,
for the interchange of like nuclei, in a manner dictated by the nature
of the spin of the nucleus. It turns out that the spin of the nucleus, or
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 statis
tics; those of the second type, such as Of 6 (with zero spin) andH 2
(with
unit spin), are said to follow BoseEinstein statistics.
The effect of an interchange of like nuclei on ^toU1 will now be ana
lyzed. Then 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
nuclei of a diatomic, or linear, molecule by imagining this exchange to
occur as a result (1) of an inversion of all the particles, electrons and
nuclei,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
already know that on the total wave function, for 2+ states, is
its effect
of the g type, to leave the total wave function unchanged for even values
of J and to change its sign for odd values of J. For u states this con
clusion is reversed. Thus, since the twostep process is 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. Symmetric or antisymmetric behavior with regard to
this exchange by an s or an a.
is indicated
For molecules, such as O u C0 16 that have identical nuclei with ,
FIG. 59 The rotational energylevel diagrams for linear molecules with like nuclei.
The statistical weight factor due to the nuclear spin is shown. In (a) the like nuclei have
/ = 0, in (b) they have / = if.
5 €>
$ %
A
U .3
.a tu
ra .
/ 5i y 85
(5 a) 5 a 3 ft Ortho
4 « 1 4 « 1 f Para
(3 a)— 3 a 3 ft 0rtho
2 « 1 2 8 1 ft Para
(1 a) 1 a 3 ft Ortho
"0 « 1 « 1 ft Para
16 16
O CO type H2 type
(a) (b)
102 INTRODUCTION TO MOLECULAR SPECTROSCOPY
*.lMv(a/3  /3a)
Since three spin functions are available to provide the correct symmetry
for the odd J whereas only one spin function makes the total wave
levels
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
weight of 1. Thus, in addition to the 2 J + 1 multiplicity that all
levels have, the odd J
have an additional multiplicity factor of 3
levels
while this factor is only 1 for even J levels. Again this alternation in
multiplicities, which leads to an alternation in populations, illustrated
in Fig. 59, cannot be observed in rotational spectra but, for molecules
like HC=CH that will be discussed in Sec. 74, an alternation in the
intensities of the rotational components of rotationvibration absorption
bands is observed.
One should recognize that the analysis given above has led us to
recognize the ortho states of RYlike molecules, which are those having
parallel ]\ nuclear spins, and the para states, which have opposed ][ nuclear
spins. A
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 dissoci
ated. One should notice that the selection rule s < s, a< > o, — —
103
ROTATIONAL SPECTRA
+ «_)_» — <+
\ >
t
— which applies to any diatomic
, molecule, elim
ca'n be combined with spin functions to give total wave functions with the
symmetry required by the nuclei. Again, however, the s and a states,
with even and odd J values, have different statistical weights.
SYMMETRICTOP MOLECULES
tion can be applied to give the allowed rotational energy levels. A state
FIG. 510 Examples of symmetrictop molecules, i.e., those with U?* In = to.
(I
4
< /„ ; prolate symmetric top; (1A > lB ; oblate symmetric lopj
104 INTRODUCTION TO MOLECULAR SPECTROSCOPY
ment of the selection rules will then allow the spectral transitions to be
drawn in and a comparison with observed spectra to be made.
where pA Pb, and p c are the angular momenta about the three axes.
,
"&+#. + ft ("•)
VJ(J + 1) £ J = 0, 1, 2, . . . (20)
where the plus and minus values correspond to the possibility of clock
wise and anticlockwise rotation about the unique axis. These quantum
restrictions lead to
and (22)
and (23)
tJK — ,^ +
&* 2 cIb
1
)
+ (8^8^r> 2
cm"
the energy. The energylevel diagrams for these two cases are shown
schematically in Fig. 511.
It should be pointed out that the occurrence of in Eq. (24) as a K
squared term leads to the same energy for a state with positive or nega
tive values of K. Thus all levels with =* K
are doubly degenerate.
AJ = 0, +1 AK = for Z^
and (25)
AJ = + AK = for K =
For an absorption experiment, the part of the selection rule that cor
responds to an increase in the energy of the system and is appropriate is
AJ = +1 AK = (26)
The fact that electromagnetic radiation cannot induce a transition
between different K
values can be understood from the fact that, for the
molecules considered here, rotation about the figure axis contributes
no rotating dipole moment. This component of the rotation cannot,
°
~6 e
4 4
> .
*• t 4 3 £
^ 8.
—
Q E
o
o O
3£
*» IS « IO ^
J: «>
a*c
> E
o o
T OS
P> C
1^
£ \
SI
107
108 INTRODUCTION TO MOLECULAR SPECTROSCOPY
K(AK = 0) 1 2 12 3 l2 3
I
\i 0v\ 0v\l/
I I I I l_
FIG. 512 The effect of centrifugal distortion on the rotational transition absorptions
of a symmetrictop molecule according to Eq. (28). (From G. Herzberg, "Infrared and
Raman Spectra," D. Van Nosfrand Company, Inc., Princeton, N.J., 1945.)
v = 2B(J + 1) cm 1
(27)
FIG. 513 Part of the J = 8 —* 9 transition of CF 3 CCH showing the effect of centrifugal
distortion. (The diagram is centered at about 51,800 megacycles/sec.) [From W. f.
ASYMMETRIC MOLECULES
— +^ #: + #.
Va
27 A
i
P%
21B
, Vl
21 c (29)
110 INTRODUCTION TO MOLECULAR SPECTROSCOPY
shift the energy levels and would not eliminate any of the allowed states.
This "adiabatic" argument shows that, even for an asymmetrictop mole
cule, the 2/ + 1 states will still exist for each value of J. A difficulty
in characterizing these states arises in the asymmetrictop case because
there no quantized component of this total angular momentum; i.e.,
is
In this way, the interconnecting lines of Fig. 514 are drawn. The J
value of any line remains unchanged, and the index t can be entered as
a subscript to each J value as shown.
The labeling of the asymmetrictop energy levels in Fig. 514 sug
gests an alternative to the use of t. One can notice from that figure
that the value of t is related to the K values of the symmetrictop mole
FIG. 514 A correlation diagram illustrating the energylevel pattern for asymmetrictop
rotors. (From W. Gordy, W. V. Smith, and R. F. Trambarulo, "Microwave Spectroscopy,"
John Wiley & Sons, Inc., New York, 1953.)
Oblate Prolate
symmetric top Asymmetric top symmetric top
112 INTRODUCTION TO MOLECULAR SPECTROSCOPY
cules according to
With this recognition one can identify an energy level with the notation
as J, or with the K notation as Jk .k „ Thus a level 3_2 with the
, .
prolate'
,
oblate
•
K
= 2[BUA + C)]
A C
where A, B, and C are the rotational constants
A = 5JV cm 1
etc. (33)
One can readily verify that for an oblate symmetric top with
Ia> Ib = Ic
Chem. Phys., 11 27 (1943)] for the energy levels of some of the lower
:
Exercise 57. Using the expressions of Table 54, plot to scale the first
several correlation lines of Fig. 512.
in the order of J; i.e., an energy level with a higher value of J may occur
at lower energy than that corresponding to a lower value of J.
Selection rules for the t values have also been given. These depend
on the components of the dipole moment of the molecule along the
directions of the principal axes. The selection rules themselves, and
their derivation, are sufficiently elaborate so that it is adequate here
TABLE 54 Some Closed Solutions for the Rotational Energy Levels of Asym
metric Tops
Ooo
lio A +B
ln A +C
loi B +C
2M '
2A +2B +2C +2 V(B  C) s + (A  C)(A  B)
2*i 4A +B+C
2,i A + IB + C
2„ A +B +4C
2o2 2A+2B +2C 2 V(B  C)» + (A  C)(A  B)
3 30 5A + 5B + 2C + 2 V4(A  By + (A  C)(B  C)
3 31 5A +2B +5C +2 V4(A  C)' — (A  B)(B  C)
32, 2A + 5B + 5C + 2 V4(B  C)» + (A  B)(A  C)
3 S2 4A + 48 + iC
3i 2 5A + 5B + 2C  2 V 4(A  B)* + (A  C)(fi  C)
3i„ 5A + 2B + bC  2 VA(A  C)  (A  B)(B  C)
1
PRINCIPAL REFERENCES
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
of these coordinates. Any additional displacement or velocity, beyond
these 3w, that imposed on an atom, or on the molecule, could be
is
where the springs have been assumed to obey Hooke's law and to have
force constants k xand kv [It should be noticed that the spring system,
.
for small displacements, is such that the restoring force in the x direction
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 poten
tialenergy expression of Eq. (1) leads to this result by forming
J' =  ~ k**
(j^r
and
/. Kv]
\*v).
The motion of the particle can now be deduced by applying La
grange's equation to the coordinates of the system. For the x coordi
nate, the equation
1(^ +^=
dt\dx) ^ dx (3)
gives
mx + fcjX = (4)
where
'• = «T \P (6)
my + kyy = (7)
where
*v = */^
2*
0)
to motion for which the cartesian coordinates of all the atoms of the
molecule will execute simple harmonic motion.)
Exercise 61 Consider a spring system like that of Fig. 61 with
. = 1 M
atomic mass unit equivalent to a hydrogen atom, k x = 1 X 10 8 and
k y = 2 X 10 6 dynes/cm, values that are of the order of magnitude
encountered with chemical bonds.
Calculate the classical natural frequencies of this system.
(a)
(b) Draw a diagram
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
tions of this system?
in advance the directions along which the springs lay and, therefore, did
not 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, there
fore, what atomic displacements will lead to normal modes of vibration.
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 orienta
tion of the system are labeled x' and y' as in Fig. 62. The essential
differencebetween the axis choice of Fig. 61 and that of Fig. 62 can be
recognized by considering the restoring force that would act for displace
ments along the coordinate axes. In Fig. 61 it is clear that displacement
FIG. 62 The spring system of Fig. 61 described by an awkward coordinate system such
as might be used if the directions of the springs were not initially known.
,,¥
9X
]20
INTRODUCTION TO MOLECULAR SPECTROSCOPY
(id
is
(12)
t = im(x')* + iMy'y
coordinate now gives, with Eqs. (10) and
Lagrange's equation for the x'
(12),
(13)
ma?  k'j!  Ktf =
and, for the y' coordinate,
(14)
my'  KX  Kv'  o
convenient than those of Eq. (4)
Although these equations are clearly less
solutions, where the
and Eq. (7), we can again look for vibrationtype
frequency of vibration is v, by trying the functions
Differentiation twice with respect to time gives functions for x' and y'
v = ± /
(*: + K) + kk k'y y + 404)?
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', the potentialenergy function is
V = (1.25 X 10 6
)(z') 2
+ VI X lW{x'){y') + £(1.75 X 10 B )(y') 2
(a)Calculate the natural frequencies of the system, and see that the
same values are obtained as 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.
are not initially known, solution of the problem can be carried through
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.
h2 a 2
&r 2 dQ?
3n6
h2 Y* d 2 J/
(21)
where the X's are coefficients that depend on the force constants of the
molecule.
Equation (21) can now be written as
3n6 3n6
 £ X H+ X (5
x,<2,?
)
* = ** (23)
* = *l(Ql)*l(Q0 • • • *3»,(<23„6)
or
(24)
124 INTRODUCTION TO MOLECULAR SPECTROSCOPY
and substitute Eq. (24) into Eq. (23). When this is done and the entire
equation is divided through by $, one gets 3n — 6 expressions of the type
or (25)
Ai> = ±1 (26)
to = +1 ( 27 >
FIG. 63 The energylevel patterns and schematic representations of the corresponding
vibrations and a schematic infrared absorption spectrum of HsO.
600 cm
126 INTRODUCTION TO MOLECULAR SPECTROSCOPY
rotation about the axis, and this operation is also shown in Fig. 64.
It should be pointed out that the numbering of the atoms will be kept
unaltered by symmetry operations; only the displacement vectors will
undergo the symmetry operation.
That symmetry and normal vibrations are related can be readily
illustrated by reference to the spring system of Fig, 65. If one were
FIG. 64 Two symmetry elements of COi: o plane and an axis of symmetry. Symmetry
operations corresponding to these elements transform the solid arrows into the dashed
arrows.
cule, which has, therefore, some higher potential energy than the equi
librium configuration, the distorted molecule that is obtained by the
symmetry operation will have the same potential energy as the original
distorted one. This is illustrated in Fig. 66a. In a similar way, if a
molecule has kinetic energy as a result of motion of its atoms, a symmetry
operation cannot change this energy. This is apparent in Fig. 66, where
the velocities of the atoms are represented vectorially and the symmetry
operation changes the directions of these in space but does not affect
the magnitude of the velocities of atoms of given masses. It follows
then that a symmetry operation, since it does not alter the potential or
kinetic energy of a molecule, does not alter the total energy.
In the previous section it was shown that the vibrational energy
is most simply expressed in terms of the normal coordinates of the
molecules. In these coordinates both the kinetic and potential energies
contain only squared terms; i.e.,
FIG. 65 A twoparticle spring system with a plane of symmetry perpendicular to the
axis of the springs. Distortions are indicated that are {a} symmetric and (b) antisymmetric
with respect to the plane of symmetry. The arrows indicate the initial motions of the par
ticles that would follow such displacements.
Plane of symmetry
LwwB/SAA/1 IaA/S/B^VW
(a) (h)
128 INTRODUCTION TO MOIECULAR SPECTROSCOPY
Distorted
position
J~
Reflection
through
—Diane of7*
symmetry
fnj
Reflection
through
plane of
symmetry
CM
FIG. 66 Illustration that a symmetry operation does not change the potential or the
kinetic energy of a molecule.
vectors such as those of Fig. 64 or 66. In view of Eq. (28), however,
it is seen that for the energy to remain constant, in the general case
where all X< are different, when a symmetry operation is performed,
each normal coordinate must remain unchanged or, at most, change sign.
Thus, <= of Eq. (28) is unchanged if as a result of a symmetry operation
FIG. 67 Arrows indicating the relative motions of the atoms of COa in two normal
vibrations with displacements along the molecular axis.
THE VIBRATIONS OF POLYATOMIC MOLECULES 12?
rotation of the molecule, and are such that they are left unchanged or
result in a simple change of sign, i.e., of direction, when a symmetry
operation is performed. For simple molecules with a high degree of
symmetry, as for C0 2 one can often write down immediately the form
,
where the equal potential energy coefficients have been designated Xi.
Qi » aQ x + bQ t
and (32)
considered.
In summary, the behavior of normal coordinates with respect to
symmetry operations can be stated as
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 displace
ments of the atoms of the linear molecule CS2 and the bent molecule H2S
in the normal vibrations of each molecule.
PRINCIPAL REFERENCES
133
134 INTRODUCTION TO MOLECULAR SPECTROSCOPY
DIATOMIC MOLECULES
Av = +1 AJ = ±1 (1)
(2)
One should note that in these expressions the value to be inserted for J
isthe 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
expressions show, that there should be a set of absorption lines, spaced
by the constant amount 25, on the highfrequency side of the band
center, which occurs at v = u, and a corresponding set on the low
frequency side with a similar constant spacing. There should, further
more, be a gap in the band center corresponding to the absent AJ =
transitions, all of which would have had a frequency <a. It is customary
to label the lowfrequency set of lines as the P branch of the rotation
The general shape of this experimental curve is, in fact, that predicted
on the basis of Eqs. (3) and (4) or Fig. 72. It is clear that the frequency
of the v = 0,J=0tov = l, J = transition can be deduced from the
central gap band and that this value gives the spacing of the vibra
in the
tional energy levels of the molecule. Furthermore, the separation of the
components of the P and R branches can be identified with the molecular
quantity 25. From this quantity, values for the moment of inertia
and the bond length of the molecule can be deduced as they were when
the spacing of pure rotational lines was determined from studies in the
microwave region.
136 INTRODUCTION TO MOLECULAR SPECTROSCOPY
Energy
;k
'
'
u = l
.i
Energy levels 
00
"5
10 '5 a '8 '5 to 00
1 1 1 + + + +
la. i=> i& i& i& i& l& 1%
II II II ii ii ii II II
l« i» i* l<u \1l
< < < < < <1 < <
20B
12B
6B
IB
1
1
1
_
*
2fi
Spectrum <
(P branch) (A branch)
FIG. 72 The transitions that lead to rotational structure in a vibrational band for a
linear molecule based on the assumption that B is independent of y.
Two features illustrated by the HBr example in Fig. 73 have not
yet been accounted for and must now be considered. First, the relative
intensities of the components remain to be investigated and, second, the
fact that the spacings of the components are not found to be exactly
constant must be dealt with.
5
S
o
uojsniusuej) jure J»d E
137
138 INTRODUCTION TO MOLECULAR SPECTROSCOPY
B, = B,  a.(v + i) (7)
R branch, J — J + > 1
P branch, J —* J — 1
FIG. 74 An illustration that the rotational spacing and, therefore, the moment of inertia
in the v = 1 and v = states can be deduced from the rotational structure of a vibration
rotation absorption band. The difference in frequency of the components shown as heavy
solid lines gives the spacing in the v = 1 state, while the difference in the frequency of the
dashed lines gives the spacing in the v = state.
J
4
=1
1 ) ,
* 4
i
t !
i
I
i
_ t I _
I
I
i
I !
i
1 1
1
1 '
I i
i
i I
1
i i
!
1
i
I
I
o =
i
1
i
i 1
1 i
ROTATIONVIBRATION SPECTRA Ml
Thus forP and R components that start from the same J value, one has
9b(J) ~ 9p(J) = 25 (2J + 1) X (10)
are given in Table 71. 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
corresponding to the minimum in the potentialenergy curve. One
should particularly notice that r t is significantly different from r . This
difference makes itself known when one uses isotopic substitution, as was
mentioned Chap. 5,
in to obtain additional momentofinertia data for
polyatomic molecules from which additional bond lengths or angles
can be determined. The assumption of constant bond length with
isotopic substitutionwould appear to be valid to a very good approxima
tion for the equilibrium bond length. For the v = state, which is
could be used to calculate B and two that could be used to calculate Si.
LINEAR MOLECULES
6
c
a
_o
ee
oc
o
q
z
o
oc
o
<
8 S d
UOISSIIUSU&ll IU» J9J
143
Tfh
the same for 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 out that, in contrast to the situation that
exists in pure rotational spectroscopy, linear symmetric molecules can
exhibit rotationvibration absorption bands even if the molecule possesses
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, —C^C—
are examples of vibrations which lead to rotationvibration absorption
bands. From analysis of such bands, momentofinertia data for these
nonpolar molecules can be obtained.
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
°—
5 — 1
»= 1
4—4.
T , (antisymmetric
stretching
vibration)
2 J..
^Nmhpf
7— It' "I"
I
5 J I
3 444U—
!._,,
FIG. 76b A parallel band of the linear molecule CO2 which has a center of symmetry
and like atoms which obey BoseEinstein statistics.
100
E
M
C
s
146 INTRODUCTION TO MOLECUUR SPECTROSCOPY
7
5——
A
3 j r
2 1 __
1 t
o "
lift
5 1
4 — j
3 1
j FIG. 77a The energylevel diagram and transitions
2
l
1
I
i
!
of a molecule like H —Cs=C— H.
At; = +1 AJ = 0, +1 (12)
I
E
E
i
o
s
.c
6
i
X
o
1o
5
E
o
2
<
would all have the same frequency Po The fact that Si is somewhat
smaller than B leads to a slight decrease in frequency of the Q com
ponents with high / values. The Q branch usually, therefore, has a
slight asymmetry.
vibrations of a linear molecule are, as mentioned
The perpendicular
doubly degenerate, and the two perpendicular motions of the
in Sec. 64,
molecule can be coupled to show that in this vibrational state the molecule
has angular momentum as a result of this vibrational motion. This
angular momentum about the figure axis leads to some additional fea
tures of perpendicular bands. The lowest J value for the v = 1 state,
for example, is J = 1 because the one unit of angular momentum that
FIG. 78 A perpendicular band of the linear molecule N 20. (The two satellite Q
branches can be attributed to NjO molecules that are in a vibrational^ excited state.)
100
SYMMETRICTOP MOLECULES
AK = AJ = 0, ±1 if K *0
and
(13)
AK = AJ = ±1 if K =
These rules can be combined with the energylevel expression, Eq.
(14) in Chap. 5, for the rotational energies of a symmetrictop molecule
of K will be almost
spacing within each set of levels with a given value
150 INTRODUCTION TO MOLECULAR SPECTROSCOPY
V
,//
J
FIG. 79 Vibrations of symmetrytop molecules that lead to (a) parallel absorption b ana's
and (b) perpendicular absorption bands.
ROTATIONVIBRATION SPECTRA 151
the same since they are governed by the same term, the J(J + l)Bi
i.e.,
FIG. 710 The energy levels of a symmetrictop molecule and the transitions that are
allowed for a parallel band.
J
11
10
8
7
6
5
4.
3.
2.
4=
f
10"
K4
K=3
K=2
K=l
K=
1
J_L I . L I 1 I I I I i
I— K = l
Ml 1 I 1 1 I i L i i I 1 I I i i ,
K=2
i 1 1 1 I I 1 1 i
L iii K=3
1 1 1 1 1
Jh. J ———————
I I I I I i
«T =4
'
K =5
^nULUlh.iLilUUu^
FIG. 71 1 The components of a parallel band showing the contributions from each of the
K levels of the v = state.
the unique axis of the molecule are shown in Fig. 79b. For such vibra
tions, the selection rule for rotational transitions accompanying the
vibrational transition is
AK = ±1 &J = 0, ±1 (15)
S S , 3 8
uoisnuKueji lim J»d
FIG. 712 A parallel absorption band of the symmetrytop molecule
CHsBr. The P
branch is partly resolved, while only the contour of the
ft branch is obtained.
154 INTRODUCTION TO MOLECULAR SPECTROSCOPY
all the AJ = 0, +1 K.
transitions that occur for a given change in
Thus, as shown in Fig. 714, for K = *
1, the P, Q, and R type sub
The energy levels of a symmetrytop molecule showing the transitions that are
FIG. 713
allowed for a perpendicular band.
/
7
K=
+ 1 + I + I +
II II II II II II II
* * « * X ^ fetj
o
I.
a
o
o
a.
E
8 £
» S
.C M
• o
e „ II
*7 >
II II II
I h^ A)
. c
O
_ *•»
u O
155
156 INTRODUCTION TO MOLECULAR SPECTROSCOPY
curve of Fig. 715 shows, usually reveals the Q branches of the subbands
superimposed on an unresolved background.
The spacing of these Q branches can be calculated from the energy
level expression
For AK = +1
P 0ta .nch„ = &+(A + l)  K*\ B)[(K 2
ForAK= 1
Sflu—. = «+ (A  5) (K  \y  K*
= + S, (A  B)  2(1  B)K for K = 1, 2, 3,
(18)
(a) Make two energylevel diagrams, like that of Fig. 79, for CHsBr.
(Draw the rotational spacings to scale for both the v = and v = 1 states,
157
158 INTRODUCTION TO MOLECULAR SPECTROSCOPY
PRINCIPAL REFERENCES
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 must be
symmetric or antisymmetric with respect to any symmetric ele
either
ment. Furthermore, the previous chapter has shown that, for a sym
metrictop molecule, the appearance of a rotationvibration absorption
band determined by the symmetry nature of the vibration. In
is
Chap. moreover, we will see that the wave functions that describe
11,
the behavior of the electrons of a molecule must conform to the symmetry
of the molecule and that the symmetry properties of the electronic states
of a molecule provide an important and helpful characterization of the
states.
A systematic study of the symmetry properties of molecules will
now be undertaken. To avoid a rather abstract treatment, applications
of general methods and results will continually be made to the study
of the vibrations of 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 molecular
structure studies. Vibrational modes merely provide, in view of our
studies of the previous chapters, convenient illustrations of the applica
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
t
Symmetry elements
Symmetry operations
Symbol Description
E Identity No change
a Plane of symmetry Reflection through the plane
i Center of sym Inversion through the center
metry
C, Axis of symmetry Rotation about the axis by 360/p deg
Rotationreflection Rotation about the axis by 360/p deg followed by
axis of symmetry reflection through the plane
MOLECULAR SYMMETRY AND GROUP THEORY 141
RG. 81 Some of the symmetry element* in term* of the examples nansdichloroethane,
carbon dioxide, and aliens.
cbc,
162 INTRODUCTION TO MOLECULAR SPECTROSCOPY
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)
c, E CH,—CHClBr
cs E t Cs H 0,
2
D sk E, C 3 3C 2
, (perp. to the C, axis), BC1,
3ff„, a\
Da E, C 4CS
t, (perp. to the C» axis), C H,
4 (cyclobutane)
4*r„ an, Ct and St (both coinci
dent with C 4 ), i
D,» E, C t 6C, (perp. to the C« axis),
, C«H 6 (benzene)
6ff„ an, C t and C, and So (all co
incident with the C« axis), t
D.* E> C„, «> C s (perp. to the C„ axis), H,, CO,, HC=CH
<*>a„ ah, i
C2
\C
FIG. 82 The symmetry elements of H 20, point group d„ and CHjCI, point group Ci,.
(The coordinate systems are drawn in ways that will be convenient for later treatments.)
elements for all the point groups. It is, at this stage, sufficient to notice
particularly those of the C 2„ and C dv groups since molecules of the type
H 2 and CH which belong to these point groups, will be used in later
3 C1,
£
Translation in the Y Rotation about the principal axis
direction (T ) in the Y direction (R„)
FIG. 83 Representation of the translation T„ and the rotation R„ of the H2O molecule by
means of displacement vectors.
in Fig. 83. Also, since the features associated with degenerate vibra
tions are then encountered, the molecule CH 3 C1 is also used as an illus
tration and the three translational motions are represented by vectors
along the atomic cartesian coordiriates in Fig. 84.
Let us first consider the effect of the symmetry operations on the
molecular motions of the H 2 molecule, which is an example of a molecule
with no degenerate motions. The symmetry operations corresponding
to the various symmetry elements can be performed on the displacement
vectors such as those of Fig. 83. When this is done for the illustrated
motions Ty and Ry for H 2 0, one sees that the displacement arrows
either are left unchanged or are reversed in direction. These two
possibilities are represented by +1 for the symmetric result of no change
or —1 for the antisymmetric result of a reversal in direction. In a
similar manner, a +1 or —1 can be associated with the result of each
symmetry operation acting on the displacement vectors that correspond
and rotations of the H 2 molecule. (As the
to the remaining translations
CI
y
s
^7
.'S
T,
MOLECULAR SYMMETRY AND GROUP THEORY 165
and
C,(fl,) = (D(B,) (2)
With this procedure one recognizes the reason for the use of +1 and —1
to represent symmetric and antisymmetric behavior. When degenerate
motions are considered, it will be recognized that the +1 and —1 trans
formation factors that appear in the H 2 example are in fact onebyone
matrices and are examples of what are known as transformation matrices.
FIG. 85 Displacements that correspond to possible vibrations of the H2O molecule.
.Or**
^H H ^H n^ H H
166 INTRODUCTION TO MOLECULAR SPECTROSCOPY
energy levels because the moments of inertia about the axes in these two
directions must be identical. Similarly, certain vibrations of such mole
cules will necessarily have, as a result of the molecular symmetry, iden
tical energylevel patterns. It follows, as we now see, that such
will
degenerate motions must be treated as a set and that, when symmetry
properties are 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 .
FIG. 86 The effect of the symmetry operations on the translations Tx and Ty of the Cj,
molecule CH3CI. 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\
*~TX
Operation oj
Similarly, the result of rotating the Ty vector by 120 deg can be described
as _
C»(Ty ) = + ?£ (T  x)
I
(T y) (4)
*(£)(;!£ if)®
In a similar way one can describe the effect of the symmetry operations
corresponding to the remaining symmetry elements of the C 3 , group by
transformation matrices. Thus one writes, with the aid of Fig. 86, for
all the operations of the C3,, group
* Only a few features of matrix methods are necessary for the treatments given
in this chapter. The student with no background be able to
in this subject should
follow the developments if he learns matrix multiplication enough to understand
equations like Eq. (5).
168 INTRODUCTION TO MOLECULAR SPECTROSCOPY
_ V3\
2
1
1 1 1 1 T.
1 1 1 1 R,
1 1 1 1 Rv) Tx
1 1 1 1 Rx , T„
MOLECULAR SYMMETRY AND GROUP THEORY 169
Ax 1 1 ,1 1 T.
A, 1 1 1 1 R.
Bx 1 1 1 1 Ry, T*
B, 1 1 1 1 Rx, Ty
''
73
a ^* '
*
° 6i s as
•
s  a
03
6," a* &,
8a a
.
^ w h 1 +
^b" 1 > 1 IN ICC 1
i
>r
i
<*i win
w ~~ + +
Q. ~b° 1 h I IN ICO 1
o
s i >r
e
+
"5
,^^
o h
iH i— 1 
j»
b 1
o
+
N 
r\ t* 1 in
'
i i
1 1
o*
i
>r
+
£
O
*>l«
<\ l IIN
o
5 + 1
o '", rt
— N 1 ICO 1
i >r
i
^^
o—
Kl .1 rH
+
H O
+
00
V—
a
CO
»
< o
170
MOLECULAR SYMMETRY AND GROUP THEORY 171
1 1 1 1 1 1 T,
A, 1 1 1 1 1 1 R,
E 2 1 X (R„,Ry), (T„,Ty)
triply degenerate set as F or T. (It will, in fact, be seen later that each
entry for the nondegenerate species in tables such as Tables 84 and 85
is really to be interpreted as the sum of the diagonal elements of the
transformation matrix. If the matrix is a onebyone matrix, this is, of
densed Form
A, 1 1 1 T.
At 1 1 1 R,
E 2 1 (Rx,Rv)t (Tx,T v )
172 INTRODUCTION TO MOLECULAR SPECTROSCOPY
1948. The first of these references also gives a detailed discussion, with
many 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
matrix, these tables summarizing symmetry behavior are known as the
character tables for thesymmetry 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 devel
oped 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
completed. 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
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
of properties of symmetric molecules. The theory can, for example,
deal with the symmetry operations that have been treated in the pre
ceding 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
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
operations provides material with which some of the general grouptheory
results can be illustrated.
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
the combination procedure multiplication although, as 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
isthat there be a rule which makes the combination PQ meaningful and,
moreover, makes PQ equal to an element of the group.
2. The must hold for the combination of elements.
associative law
Thus if P(QR) means that Q and R are multiplied, i.e., combined accord
ing to the appropriate rule, and then P multiplies the element formed
from QR, the associative law requires
The righthand side implies that P and Q are first combined and that the
element they form is then combined with R..
(It should here be mentioned that the commutative law will not
EP = PE = P
EQ = QE = Q (7)
ER = RE = R
and so forth, for all elements of the group. (Note that the element E
does commute with all elements of the group.)
4. For every element of the group there must exist an inverse which
is also an element of the group. An inverse is defined so that if S, for
example, is the inverse of Q
QS = SQ = E (8)
174 INTRODUCTION TO MOLECULAR SPECTROSCOPY
EC* = C 2 <r,<ri = C 2
C*r,= <t'
v (9)
CW£ = a, etc.
We find
EC = dE = C 2
* etc. (11)
MOLECULAR SYMMETRY AND GROUP THEORY 175
C2C2 = E
w, = E (12)
oW. = E
Thus, and tb^is will not generally be so, each element of the C 2v group
is its own inverse, and the fourth requirement is satisfied.
We
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.
Any deduction that can be made about the elements of a group is,
to be put is the fact that the elements of a group, such as the symmetry
operations of a molecule, can be represented by numbers, or more gen
erally matrices, and these can then be combined by ordinary multiplica
tion. For the representation to be trice, or faithful, the multiplication of the
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
r 4 can be given as
E c2 a.
/
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 opera
tions is always faithfully represented.
The operation C 2 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
In this way one sees that, if C2 is representedby (—1) and <r„ by (+1),
the combination C*r v is represented by the simple multiple
(+1)(1)  (D
Furthermore, since as Table 84 shows, the operation <r'v on T x changes
the direction of the Tx displacement vectors, one represents (r'v (Tx) by
( — 1) Tx . This example shows that, if C s and a, are represented by trans
formation matrices, the product CV, = (r'„ will be properly represented
by the product of the transformation matrices of C 2 and <r v It follows, .
E c2 o»
GO'
/l
G ?) G ?) G
0\ /l 0\ /l 0\
(lit) (O 10} (o 1 o) 1 o)
\0 1/ \0 1/ \0 1/ \0 1/
G!) (J t) G ?) G 0
and so forth. Again one can verify that these form faithful representa
tions of the group C 2v .
FIG. 87 The effect of the <r„ symmetry operation on the 3n cartesian displacement
coordinates of" H 2 0. One sees, for example, that xh transforms as shown into x»< and
that x H = xh>.
4
Operation SO.
ZB' xii
"»^H*
MOLECULAR SYMMETRY AND GROUP THEORY 179
formation matrix
'
Xh 1 '
xH
Vh 1 Vh
zh 1 zh
xH '
1 Xh'
Vh> = 1 Vh'
zh' 1 Zh'
x 1 Xo
y« 1 y«
«o , .0 1, .
zo
A' = 0r l A0
B' = p~ Bpl
(17)
C = jS'CjS etc.
and obtain
p l AWBp = p~ l D0 (19)
fl •
°
8 : = E =  1 (20)
Q I J ;
Now we can multiply both sides of this equation, on the left by /3 and
on the right by p~\ Since /3/3 1 = p~ l P = E, one has
AB = D (22)
'(ai)
a (o 2)
(a,)
(23)
/(&i) •
•
\
B' = (
(ft,) •
\ (6 3 ) • •
7 etc.
where oi, fti, c h are square matrices of the same dimension, o 2 62, C2
. . . ,
are square matrices of the same dimension, and so forth. If such trans
MOLECULAR SYMMETRY AND GROUP THEORY 181
AB = D or A'B' = D'
'
becomes, since matrices are equal only if their corresponding elements are
equal,
ai&i = di
0262 = ds (24)
03&3 = <^3
XB ri(fl)iyfl) = o
Vr (25)
1 (/j)r,(«) = o etc.
182 INTRODUCTION TO MOLECULAR SPECTROSCOPY
I* T^RMR) = 4
(27)
XR r 2 (R)T 2 (R) = 4 etc.
or of T 2 gives the value 6, the order of the group. However, the sum
of the squares of any component of the matrices of r 3 the
,
entries in the
first row, column, for example, gives the value 3, the order of the
first
v= i^j
Ir R
i (i2) m „rJ (i?) m o
(28)
I URUURU =  ( 29 )
MOLECULAR SYMMETRY AND GROUP THEORY 183
where g is the order of the group and U is the dimension of the t'th irreduc
ible representation.
Q = pWe (32)
then
xq = xp (33)
where /3' indicates the transposed /S matrix. Equation (34) can now be
written as
Qu = I 0»)*G8)kP« (36)
kl
Qu = G9)*0»)« p «
X
i
J
i,k,l
= 22 Kfl*G8)«l p«
kl i
— 2 &tiPw
= ZP» (37)
has been used to express the result of £ (j8)«(/S)k which corresponds to the
i
xq = xp (38)
o (
and
X»(«)»(«).=
R
ff (40)
Exercise 88. Verify that the characters of the C 2 „ and C 3t groups, given ,
in Tables 84 and 86, behave in the manner indicated by Eqs. (39) and
(40).
Exercise 89. Verify that the C 2t> and C 3„ group characters behave
according to Eq. (44).
810. Classes
X~ PX l
and X~^QX
where X is in turn all the elements of the group, gives a result which is a
member of the set, i.e., is P or Q.
This general definition can be applied to C 3 and C\ to show that they
constitute a class in the group C 3l) . The following combinations are
investigated, and the operation to which they are equivalent is noted
E*C 3E = C 3 E~aE i = a
Cj 1 C 3 C 3 = C 3 ^C\C 3 = C 3
(Cfl'CCJ = c\ (CIV'CICI = C\
P7K7*r. = CI = C
ff^CJir, 3
= C\
(oi)>C*: (O'CX = c 3
(O'cv: = c\ 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.
,
of a class have the same characters. The matrix of each member of a class
is transformed into another member of the class by at least one of the
transformation matrices. It follows that these two matrices must have
the same character. In this way all members of a class can be seen to
have the same characters for all irreducible representations.
It is this result that allows character tables to include only typical
elements of each class rather than all the elements of the class. The
number of elements in the class is, however, indicated as was done in the
Cj, and C 3v character tables.
The detailed working out of the combination X~ PX is not usually X
and
X [Vr*xt(R)]lVnixi(R)] = 9 (46)
Over
all classes
The final aspect of abstract group theory that must be dealt with
before 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 trans
x(R)  l aiK(R) W
MOLECULAR SYMMETRY AND GROUP THEORY 189
representations of the group, and the a/s are the number of times the
IR x(R)xi(R) =lt
R j=l
micmxim (48)
x(R)xi(R) = ckg
or
?
= x{R)xi ( R)
at
\ X (5o)
1
V nnx(R)xi(R) (51)
Over
all classes
group are 4, 0, — 2, +2 for the classes of E, Ci, a v Deduce the , and a'v .
of one base are linear combinations of those of the other base, the two
representations are said to be equivalent and the characters of the two
representations are equal. (The result is based on the fact that two such
representations can be shown to be related by a similarity transforma
tion.) With this theorem one can resort to the much simpler procedure
of constructing the reducible representation on the basis of the 3n
cartesian displacement coordinates. Such transformation matrices were
deduced for the H 2 molecule in Sec. 86. The character of this repre
sentation, which is found rather easily, will be the same as that for
the
XH Xh
y'n Vh
4 Zh
XH , Xh'
= Transformation
matrix
z'„, Zh'
Xfj x
2/'o 2/o
4 J 1. . Zo
E
10000000 0^1
010000000
001000000
000 100000
000010000
000001000
000000100
000000010
000000001
192 INTRODUCTION TO MOLECULAR SPECTROSCOPY
1^2
'
1 0'
1
1
1
1
1
1
1
1 (T
1
1
1
 1
.0 1
<
'
1
1
1
1
1
o 1
One should first notice that diagonal elements occur only if the sym
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 atoms that
do. not change positions as a result of the symmetry operation. With
this recognition and the fact that the vectors of unchanged atoms in
molecules like H 2 are left unchanged or are reversed and that these
effects lead to +1 and — 1, respectively, along the diagonal, one can write
MOLECULAR SYMMETRY AND GROUP THEORY 193
E C2 av
9113
The sums of the diagonal elements of the complete transformation
matrices given above confirm these values.
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 C2 operation, it will contribute a net —1 contribution
to the C 2 character. Similarly, if any atom is unchanged in position by a
reflection through a plane, it will contribute a +1 to the appropriate
a character. Furthermore, if a molecule has a center of symmetry and
an atom is situated at this center, its position will be unchanged by
inversion at the center of symmetry, all three cartesian coordinate
vectors will be reversed, and a contribution of —3 will be made to the
character. Slightly more difficult to visualize are the characters con
tributed by atoms when, as a result of a C 3 d, and
, so forth, rotation
their positions are unchanged. Figure 88 shows the geometry that leads
to the transformation matrices and the contributions to the character in
such cases.
FIG. 88 The contributions for each unshifted atom, i.e., each atom on the axis, to the
character of the 3n dimensional representation for the operations C„ and S„.
cos 6 • sin 6
sin 9 cosd
1
shown that the number of times the various irreducible representations are
contained in a reducible representation could be deduced. These results,
along with the fact that each normal mode, including translation and
rotation as well as vibration, transforms according to one of the irreduc
ible representations, allow the number of normal modes of the different
symmetry types, i.e., belonging to the different reducible representations,
to be determined.
The H 2 example can again be used. The characters of the irreduc
ible representations are given in the character table, Table 84.
The characters of the reducible representation were given in the
previous section as
B Ci av it.
911
Now one calculates the number of normal modes that transform
according to the first representation, i.e., belong to the symmetry
E 3
a 1
i 3
C2 1
C3, C3 u
ci, c\ 1
a. c\ 2
MOLECULAR SYMMETRY AND GROUP THEORY 19S
ai
M
= 
Over
>
all classes
n RX (R)xi(R)
= i[9  1 +1+ 3] = 3
Similarly,
a2 = i[9  1  1  3] = 1
a, = #9 + 1 + 1  3] = 2
and (52)
a4 = i[9 + 1  1 + 3] = 3
of the symmetry type B 2 One can verify that the displacements dis
.
which symmetry type the oscillating dipole moment will not necessarily
be zero.
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
normal coordinate Q, only if one of the integrals
fMQ<)n*MQi) dr
JMQi^vUQi) dr
or
SMQi)n*MQi) dr
follows that the representations T/x x , Tii y , and ry2 will be the same as the
representations I>„ T T „ and Tt,.
The vibrational wave function for a molecule can be described as
For the ground state, where all vibrational quantum numbers are zero,
one has
For harmonic oscillator wave functions this total wave function has the
form, in view of the wave functions of Eq. (245),
In this case, where v, = 1, the wave function for the molecule transforms
according to the normal coordinate Qi. Similarly, if a degenerate pair of
vibrations are excited to the v = 1 level, the vibrational wave function
of the molecule will transform as does the degenerate pair of normal
coordinates.
These results can now be summarized according to the effect of the
symmetry operation R as
yx
—R * V Tx (R)n x
Hy
—R > r r!/ (it)/Xj/
p. ^ Tt.(R)p. (59)
R
YWO — tf'rO
*.,! ^ T Qi (R)i Vi =i
and so forth. 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 representa
tions show that only if Y Tx and T Qi are identical representations can the
product of T Tl (R) and T Qi (R) be unity for every R. It follows that
the transition moment integral for the v = to v = 1 transition for a given
normal coordinate can be different from zero only if the normal coordinate
belongs to the same symmetry species as Tx Ty or , Tz
, .
their mass is usually so much less than that of the other atoms of the
molecule, often lead to such vibrations. It turns out that in such a case
calculate the types of the vibrations of the molecule without the two
hydrogen atoms. The characters of the reducible representation for
tljis nineatom residue can be worked out, with the aid of Table 84, to be
x 27 1 1 5
at = i[27 + 1  1 + 5] = 8
Removal of the translations and rotations shows that the representation
for the vibrations is composed of
r„ h = 7 At + 4A + 4B + 6B
2 X 2 (62)
The same treatment with the entire molecule, i.e., including the two
hydrogen atoms, gives
(This same result could have been obtained by writing down the con
tributions to the reducible representation that the two hydrogen atoms
make and then resolving this representation into the irreducible repre
sentations that it contains.)
now be drawn to represent
Pictures can the six hydrogen vibrations.
Exact indications of how the atoms move in the normal coordinates can
H
FIG. 810 Vibrations of the CH2 group classified according to symmetry. The form of
the actual vibrations and the frequencies of the fundamental absorption bands depend
somewhat on the nature of the molecule containing the CH 2 group.
f
4 j(CH stretching) .4,(CH Z bending) .^(CH.. twisting)
v = 2,870cm 1 v = l,460cm _1 v =
1,270cm 1
7 I : h
«,(CH stretching) fljtCHj nuking) * 2 (CHj wagging)
PRINCIPAL REFERENCES
"".*' 1
'
...
\
CALCULATION OF
VIBRATIONAL FREQUENCIES AND
NORMAL COORDINATES OF
POLYATOMIC MOLECULES
r = * £ «,(*,*+. # + 3) (i)
This expression is the basis for the treatment of kinetic energy in vibra
tional problems. 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&> = ° X m& =
>=i
° ( 2>
and
n (3)
204 INTRODUCTION TO MOLECULAR SPECTROSCOPY
u = i X= K(*r«)' (4)
i,i l
For H— O— H', for example, this would lead to the potential function
where 5r H o, 5r H 'o, and 5r H H' represent changes from the designated equi
librium internuclear distances. The assumption of a central force field,
therefore, reduces the number of terms in the description of the potential
energy of the H 2 molecule to two, i.e., fc H o and A; H h'.
The valencebond force field assumes that the potential energy of a
distorted molecule can best be described in terms of the changes in
length of chemical bonds and changes in angles between chemical bonds
from their equilibrium values. With this approach one would attempt
to describe the potentialenergy function of H2O by the expression
U = i/cHo(5r HO )
2
+ i/c H o(«r H'o) +
2
iMM 2
(7)
where 8a is the change in the angle between the two bonds from its
like fc H o, will have the units of dynes per centimeter. The two force
constants k a and k'a are related by k'a — k a /r\.]
As we will see later in the chapter, the absorption band frequencies
corresponding to the fundamental transitions of H2O can be used to
deduce values of the constants in the potentialenergy expression. In
fact, one can determine the two force constants in the previous potential
energy expressions so that the calculated frequencies are close to two
of the observed absorption band frequencies. The success of the poten
tial function can then be judged by how well the calculated value of the
third frequency agrees with that observed. When such calculations are
performed it is clear that neither simplified potential function is com
pletely satisfactory. The results suggest, however, that the valence
bond field is usually the preferable approach to a satisfactory potential
function.
One can, if the available spectroscopic data warrant, add additional
206 INTRODUCTION TO MOLECULAR SPECTROSCOPY
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
This function will certainly provide a better description for the 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.
ST I
Restoring force on Sa = — , . = k a (8a) + %k BO a {8r BO +
,
8r B >
)
(9)
One sees that the added terms allow for a restoring force to act on angular
displacements, not only as the result of these displacements, but also
as a result of changes in the bond lengths from their equilibrium distances.
Furthermore, seems reasonable, and turns out to be so, that interaction
it
terms, such as k H o, a should generally be small and need not always have
positive signs.
For a vibrating molecule there will be, as we will see, 3w — 6 such equa
tions. The set of these equations can be solved for the 3m — 6 vibra
tional frequencies and modes of vibration.
In order to apply Eq. (10) to a system, it is necessary that both
T and U be expressions involving the same set of coordinates. This
requirement creates considerable complexity in molecularvibration prob
lems since, as we have seen in the previous two sections, it is convenient
to set up T in cartesian displacement coordinates and U in what are called
internal coordinates, i.e., bond stretching and either angle bending or
internuclear distance type coordinates. Thus, if Ri, Rt, . . . , Rz ne
represent the internaldisplacement coordinates, i.e., the coordinates
which describe the displacements of the atoms from their equilibrium
and the bond angles from their equilibrium values,
internuclear distances
and the cartesian displacement coordinates are represented by xi, x^,
Sn6
T = l I mfbj (11)
yi
U = i £ k/RiB, (12)
t\j'i
Ri = fi(Xl, . ,Xtn)
208 INTRODUCTION TO MOLECULAR SPECTROSCOPY
molecule. 3The
degrees of freedom along this axis will lead to two
vibrations, which will involve stretching of the bonds, and one transla
tion. The more general problem of a threedimensional molecule will
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 ,
positions of the three atoms along the onedimensional line of the molecule,
as indicated in Fig. 91, the kinetic energy for the onedimensional prob
lem can be immediately written down as
T = frn&l + \m x\ + £m x§
2 3 (15)
CALCULATION OF VIBRATIONAL FREQUENCIES ,
209
i, = fi&u&t)
x2 = /,GM0 (16)
x3 = MRiA)
so that the kinetic energy expression of Eq. (15) can be written in terms
of the internal coordinates Ri and jR 2 . The two types of coordinates are
Br 12 = R = t (x 2  a:,)  r° 2 (17)
and
8r i3 = R2 = (x»  x 2)  rg, (18)
Furthermore, since rj 2 and r!j 3 are molecular properties that are not time
dependent, the time derivatives of Eqs. (17) and (18) are
Ri = Xi — ii (19)
Ri = x3  x2 (20)
In the convenient matrix notation, Eqs. (19) and (20) can be written as
1 1
X, (21)
(£)( 1 Ti
v \x%
1
One cannot immediately solve Eqs. (19) and (20), or Eq. (21), for ±i, x 2 ,
additional relation
This expression allows, with Eqs. (19) and (20), or Eq. (21), the expres
and x 3 in terms of Ri and ij 2 to be obtained. In matrix
sion for ±i, Xi,
notation one can add this additional relation to give
(23)
Now we can take the inverse of the square matrix to get, with the notation
M = mi +m + 2 wi 3 , the desired result
(m 2 +m 3)
—m 3 1
^
'zA
M M M
mi —m 1
— 3
Xi
xj
J
M M M (24)
TOl mi + m 2 1
M M M
or one can obtain, by means of the necessary algebraic manipulations, the
algebraic equations equivalent to this:
. _ (m 2 +m 3) _
Rx
m 3 _
Ri
Xl
M M
mi $ m >
X2
~M Kl ~M3JKi (25)
R
x
*~M R i+ M >
Substitution of these expressions into Eq. (15) for T gives, after rearrange
ment,
T =
^ 2
(ml + 2m,m, f mf ,+ m^Rl
+ J^k (2m\ + 2mim 3 + 2m m )EiiJ
2 3 2
and
+ 22^2 ( 2m 3 + 2mim 3 + 2m m )R + k R =
2 3 1 2 2 (29)
Ri = Ai cos 2Kvt
and
( 30)
Ri = A2 cos 25tj<<
I
4*V ^ 2 (ml + 2m 2m 3 + m\ + mm + mm,) + kA 2 Ai
tion arising from Eq. (31) along with the values of the atomic masses,
yield roots of the equation with frequencies corresponding
to the observed
values of 2,089 and 3,312 cm". In this way one deduces that the force
212 INTRODUCTION TO MOLECULAR SPECTROSCOPY
fc = HC 5.8 X 10 dynes/cm
5
,
32

JW = 17.9 X 10 dynes/cm6
Exercise 93. Verify that the force constants of Eq. (32) lead, when sub
stituted in Eq. (31), to the observed stretching frequencies of the HCN
molecule.
Exercise 94. Calculate the positions of the absorption bands due to
the stretching vibrations to be expected for DCN.
and
For v = 3,312 cm' A A2 =
x \ 1.00:  0.137 (34)
atoms of HCN
in the two stretching modes. Do this by attaching
arrows to the atoms suoh that no net translation is given to the molecule
and that
so the relative amplitudes given by Eqs. (33) and (34) are
obeyed.
Exercise 96. Deduce relative displacement amplitudes and draw suita
ble diagrams for the two stretching vibrations of DCN.
calculation was
Exercise 97. Consider the basis for the fact that some
to draw the diagrams of the previous two exercises, whereas in
necessary
CS 2 molecule could be
Exercise 63 the corresponding vibrations of the
drawn with less calculation.
CALCULATION OF VIBRATIONAL FREQUENCIES 213
tial function like that of Eq. (19) is assumed, what values of the
stretching
force constants for the C=0 and C=S
bonds are calculated?
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 C=0
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
molecule.
mentioned in Sec. 64, the necessary absence of cross terms in the kinetic
and potentialenergy expressions if these expressions are set up in terms
of symmetry coordinates. These coordinates consist of linear combina
tions of the cartesian or internaldisplacement coordinates. The com
binations are such that each symmetry coordinate is symmetric or anti
symmetric with respect to each symmetry operation. One recalls that
if and S are symmetry coordinates that behave differently with respect
Si p
to any symmetry operation, perhaps Si —> S, and S p
— > —Sp for a par
involving S SP ( must not occur in U. If such cross terms did occur, the
—
symmetry operation would convert SiSp —* —<§,<§„ and SiSp » —SiSp and
would alter the kinetic and the potential energies of the molecule. This
a o o
= (35)
o o a
o o
2m H„
m *2
S2
\
H
V
216 INTRODUCTION TO MOLECULAR SPECTROSCOPY
T = t(Si,S h S 3 ) (38)
and
U= u(Si,St,S t ) (39)
alent to xs, j/h, and so forth. Inspection of Fig. 92 allows one to write
immediately the velocities that the atoms would have along the cartesian
directions in terms of velocity contributions based on the symmetry
coordinates as
2m H <S—
Xw _
sin a * a
6 = —  .
= a  • •
= 3
S3 sin a
xB Si Si sin a; x ; <!>i
too
(40)
*** '
= S + S3
Vh = Si  S 3 cos a; y = ; V*' 2 cos a
u k BO sin 2 a + ~
2fe,
r„
cos 2 a S%
'2
+
'
fc
„ .
HO cos 2
A 2m H \
^l+ j
.
— 2
J
+71
,
2ka
sin2
. .
^i
(\
+ 2m
,
__H smajjs
\ 1 „
.
2
H 5
.
sin a cos a (l+^o.)]"'
+
Now that T and C/ are expressed, by Eqs. (41) and (44), in terms
of the symmetry coordinates S h Si, and S h Lagrange's equation can
be applied to each of these coordinates. Again three equations are
obtained, and solutions of the form
Si — Ai cos 2irrf
can be sought. Nontrivial solutions of this form are then seen to exist
if the determinant composed of the coefficients of the A's is zero.
The elements of the determinant are rather cumbersome, and it is
convenient to introduce the notation
where the 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 612
621 622 — Xfl 22 = (48)
&33 — X<l33
It is clear that the symmetry coordinates have led to the desired break
down of the 3 X 3 determinant toa2X2andalXl block. The two
218 INTRODUCTION TO MOLECULAR SPECTROSCOPY
2 \an a 2 2/ anffl2 2
fcno = 7.76 X 10 6
and
—„ = 0.69 X 10 5 dynes/cm
Exercise 910. Repeat the calculations of Exercise 99, but use the
method of symmetry coordinates illustrated here.
2U = ^k R k R kl t
kl
2U = ^fhiR k Ri
kl
W = R'FR (50)
\0 ki)
3n
2T = I m<x\ (51)
«« = (mi)ixi (52)
3n
1
23 = I « (53)
t=i
1=1
R = Bx (55)
problem.]
The expressions corresponding to Eqs. (54) and (55), but involving
the <ji coordinates, are
3n
Rh = J)
D Mq\ where D =B ki ki (m,) _i (56)
»=i
and
R = Dq
The principal problem now is to proceed from
2T = 1 mi%\ = X 9l
t=i i=i
R = Dq (57)
© = (58)
(».)
CALCULATION OF VIBRATIONAL FREQUENCIES 221
ar = (QQ
1
) (59)
1
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 ,
Now the desired inverse of Eq. (60) can, formally, be written down
as
q = SCr'CR (62)
With this relation one can express T in terms of the internal coordinates
as
2T = q'q = ^'(XrO'SCr 1 ^ (63)
and «' =
"(f) (#'r') (64)
© = 1
(QQo) and (ori) ' (66)
= (S)
to/
2T = (R'r')
(<Q (QQ a) (f) (67)
IT  (R'Q' + r'Q'„)(QB + Q f)
= ii'Q'QB + R'Q'Qor + r'Q' QR + r'Q'oQo* (68)
Since r is a zero matrix, the last three terms are zero and one is left with
2T = R'Q'QR (69)
and
wr> =
(£) ««•>  (£« S%) = '— < 71)
Now one must recognize that the internal coordinates will be the basis
for descriptions of the pure vibrations of the molecule and that these
coordinates will therefore be orthogonal to the overall translational and
rotational coordinates. It follows that D and D a are orthogonal matrices
and that DD' is a zero matrix. This relationship eliminates the second
term of Eq. (73) and leaves
DD'Q'Q = I (74)
Q'Q = (DDT* = G 1
(75)
where the usually used symbol G = DD' has been introduced for this
important matrix. 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» =
2,^ (76)
From this result we can calculate each element of the G matrix, i.e.,
Rh = A k cos 2rvt
Fu  (6»)iiX F»  (G^OiiX
F„  ((? 1 ) 2 iX ^22  (G'UX (79)
\F  ff»A = (80)
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
satisfy the equation. The ®—©— ®
molecular type example can be
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 HCN molecule, from
the given force constants, by the method of Sec. 96.
e*« = / ZT BkiBli k, I  1, . . . ,
3n  6 (82)
Rk = £• B*A (83)
i=l
+ (B kXl xt +B kVl y + 2
• • )
+
+ (B kXn x n + B kyJ n + B kz J„)
These many
products of components can be more neatly expressed by
introducing the vectors
and
sjtt with components B kx„ B ky„ B kZl
where t numbers off the n atoms of the molecule. With this notation
Rk is written as
Rk = ^ s*t •
p( (84)
< =i
(?*!=>— bm B« (85)
ti
— s*t •
su — — (B kXl B lXl +B ky ,Bi Vl + B/c^Bu,) (86)
This is the same contribution as is expected from Eq. (79), except for
the notation based on x t, y t, zt rather than on the running index i. The
formulation of Eq. (85) is helpful only if there is a convenient way of
expressing the s k vectors. t This can be done by introducing unit vectors
e a/s along the bonds in the molecule. The subscripts a and /3 indicate
CALCULATION OF VIBRATIONAL FREQUENCIES 225
the terminal atoms of the bond, and it is agreed that the unit vectors
are directed from the atom labeled a to that labeled 0.
Ska = — 6<*0
and (87)
Thus if one were dealing with the internal coordinate Ri = Sr on for the
molecule — —
H O H' and the « vector had been indicated as
/
H H'
one would have
and (88)
SlO — — «BO
If Rk involves an angle bending, Sa for H 2 0, for example, one
agrees to draw the e vectors directed away from the apex angle thus
e OH// WCoh'
More generally, one might number the three atoms that fix the value
of the interbond angle and draw the « vectors as
226 INTRODUCTION TO MOLECULAR SPECTROSCOPY
_ cos y>€ 31 — t 32
S*l = :
(89)
r» sin <p
r 31 r 8 2 sin <p
These relations between the s vectors and the e vectors, the latter intro
ducing the molecular geometry into the problem, allow, for very many
molecules, the G matrix elements to be readily calculated according to the
expression
G?w"'=
= 77 —
ZT s *<

s" ( 92 )
The dot products between the various s vectors will lead to dot products
between the e vectors that are fixed along the directions of the bonds.
In this way cosines of angles between bonds of the molecule will arise
and will, in a very convenient way, introduce the molecular geometry
into the G matrix.
coordinates Rk according to
3JI6
S = t ^ U R lk h (93)
* =i
or
8 = UR (94)
will hold.
2T = R'GiR (98)
2T = R'UWG^UWR (99)
2T = S'UGWS = S'& S l
(100)
has been introduced. Since all three matrices are nonsingular, the 9
matrix can be expressed by
8 = (£/') W 1
= UGU' (102)
This matrix equation allows, since U and are known from the way V
in which the symmetry coordinates were set up and the elements of G
228 INTRODUCTION TO MOLECULAR SPECTROSCOPY
3n6
S= I Uun* (104)
4= 1
8 „, = ^iSSS S
, (105)
i=i
With Eqs. (104) and (105) the kineticenergy matrix g of Eqs. (100) and
(101) can be set up.
Thus one calculates the various S vectors from Eq. (104) and sub
stitutes these, along with the appropriate atomicmass terms in Eq. (105),
to obtain the desired kineticenergy matrix based on the symmetry
coordinates of the problem.
The potentialenergy expression based on these coordinates pre
sents no difficulty. One can write down," except for numerical values
of the components of the F matrix, as shown in Sec. 97, the potential
energy expression
2U = S'UFU'S (109)
or
217 = S'5S (n°)
CALCULATION OF VIBRATIONAL FREQUENCIES 229
ff = UFU' (111)
With Eqs. (100) and (110) and the methods for obtaining g and ff
PRINCIPAL REFERENCES
lower electronic state and the various vibrational levels, labeled v' = 0,
1, 2, . . . , of the upper electronic state. Three factors must be kept
in mind to answer this question.
1. As observation of the vibrational structure of electronic bands
232 INTRODUCTION TO MOLECULAR SPECTROSCOPY
FIG. 101 Potentialenergy functions, vibrational energy levels, and vibrational prob
ability functions ^2 for two typical electronic states of a diatomic molecule.
Internuclear distance *
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 233
nuclear distance. (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
10"" 13 sec.) This characteristic of electronic and nuclear motions leads
to the FranckCondon principle that an electronic transition in a molecule
takes place so rapidly compared to the vibrational motion of the nuclei
that the internuclear distance can be regarded as fixed during the transition.
It 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
FIG. 102 (o) Some of the most probable transitions, for an absorption experiment at a
relatively low temperature, for the potentialenergy curves of Fig. 101. (b) Examples
of the most probable .mission transitions between vibrational levels of two electronic
states. (Note, as Table 101 shows, that for a given value of v transitions to states with
two different values of v are preferred.)
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 235
rows of the Deslandres table can now be recognized as giving the spacing
of the vibrational levels in the upper electronic state, while the differ
ences between the values in the columns give the vibrational spacing
in the lower electronic state.
It should now be clear that data from electronic absorption or
emission bands provide much more information on the vibrational energy
level pattern of a diatomic molecule than can be obtained from direct
studies of vibrational transitions. One obtains information on the ener
gies of levels with high vibrational quantum numbers, and one can learn,
therefore, much about the potentialenergy function. For example, there
isan electronic transition of I 2 that leads to an absorption band at about
2,000 A connecting the ground electronic state with an excited state.
The vibrational structure of this band has been measured in considerable
detail,and transitions involving groundstate vibrational quantum num
bers up to v" = 114 have been reported. From the data on these
vibrational spacings, some of which are summarized in Table 102, a
welldefined potential energy function can be deduced. This is shown
in Fig. 105 along with, for comparison, the Morse curve that was intro
duced in Sec. 23. (The Morse curve is generally accepted as a good
approximation to the potential function of a diatomic molecule.)
In favorable cases, such as the I 2 transition mentioned in the previ
ous 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 can be deduced by a suitable extrapolation. It is
particularly important to recognize that this information on the shape
of the potential function, and often on the dissociation energy, can be
<k o °
O S >!
X *
o £
8 7 1
1 o (3
•8  i
1—
j o
ja
o".
u
1
o
m 3 »
o to E
t» £ 2
O * 4
_g — , c
§
z «
3 JQ C C
O C
a, +
S <3
.2 6
Kl2
£ . £
P £ F=
I LI V 03
2 O *
< I E
O £ o
u_ Ji _Q
236
BeS 3UOJp33
jaddf) J3AU)
o — £
» » ;
J 2 —
' s
S08E O
H 5
IS
** to
LLS'%
° »
a S
E a o
£
Of o £ •<
—SSI'E S* D i
• e i
4) ^ D (j
5 O
6 £ S
ZZ6Z
II
^ w N ii 3 og n * o M H C O
rr e
a)
O
237
238 INTRODUCTION TO MOLECULAR SPECTROSCOPY
obtained not only for the ground electronic state but also, in contrast to
studies in the infrared region, for excited electronic states. (Some mole
cules have been studied sufficiently so that a rather detailed diagram
showing the variation of potential energy with internuclear distance
for various electronic states of the molecule can be drawn. An example
is provided in Fig. 1020.)
X 39,698.8 (1322.3)
1
38,476.5 (1307.5)
2
37,068.7
3
(1061.2)
3 41,597.4 (1309.1) 40,288.3
(1042.9)
4 41,331.2
S 41,066.1
(1015.9)
6 42,082.0
7
8
9
* From _G. Herzberg, "Molecular Spectra and Molecular Structure," D. Van Nostrand Company,
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 239
energy, i.e., the energy that the molecule would have if it were not rotat
ing and remained at the minimum of the potentalenergy curve for that
state. The symbol G is used to represent the vibrational energy of the
molecule, while F represents its rotational energy. Finally, a double
4 5 6 7
(1060.0) (1059.2)
37,712.5 (1266.1) 36,446.4 (1252.4) 35,194.0
(1043.9) (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
where B'v and B" are the rotational constants for the vibrational and
electronic states involved in the transition. In general, further complica
tions arise in that the selection rules on J depend on the types of electronic
states involved in the transition. However, one frequently has situa
tions in which &J = 0, +1 are allowed. For these rotational branches
one has, if the value of J" is simply labeled as /,
>" Ai (cm" 1 )
213.31
1
10 200.68
11
40 154.62
41
60 110.09
61
80 52.33
81
100 9.0
101
114 0.5
115
v
= ;, + 25: + (35;  5:')./ + (B'v  B'V')J 2
FIG. 105 The potentialenergy curve for the ground electronic state of h. The solid
line computed from the vibrational energy levels deduced from an electronic emission
is
band that is observed at about 2,000 A. The dashed line is a Morse curve for 2 [From l .
12,000
10,000
8,000
6,000
4,000
2,000
242 INTRODUCTION TO MOIECUIAR SPECTROSCOPY
FIG. 106 Enlargement of a component of the emission bond of Ns showing thot the
apparent 104 are in fact band heads. {Courtesy of J. A. Marquises, Cose
lines o( Fig.
3,805 A
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 243
/j 9 Rn Kl3
FIG. 107 The rotational fine structure of a component of the electronic band of Curl at
4.280A. [FromH. Schuter, H. Hohn, and 111: 484 (1939).]
H. GoHrrow; Z. Physik,
FIG. 108 A Fortrot parabola formed by plotting the frequencies of the rotational lines
of the 0~0 component of a CN band against the rotational quantum number in the lower
energy electronic state, (From G. Herzberg, "Spectra of Diatomic Mofecules," D. Van
Nostrand Company, Inc., Princeton, N.J., 1950.)
L _i_ _L J_ J_ J_
25,740 60 80 25,800 20 40 60 80 25,900 10 40

jj(cm )
244 INTRODUCTION TO MOLECULAR SPECTROSCOPY
m= — — + I, I 1, . . . , 0, . . .
,
+1 magnetic quantum num
ber
electron I as well as on n.
becomes dependent on This is shown sche
matically in Fig. 109. can be shown, however (see, for example,
It
inner shells do not upset the angular momenta associated with the
quantum numbers I and m and, for the lighter elements, do not greatly
FIG. 109 Schematic representation of the effect of filled inner shells on the allowed
energies of an outer electron.
t
i
= 4
=
*
3^
Af
Ad
Ap
4«
3d
3p
3*
n = 2
n =l Is
One electron One outer
atom electron atom
246 INTRODUCTION TO MOLECULAR SPECTROSCOPY
FIG. 1010 The shapes and orientations of the s, p, and d orbitals. Note that, rather
like the classical rotation situation, the angular momentum along the field direction is
greater the more the orbital projects out from the axis in this direction.
;=±2
2 d .
m = ±l
—^g m=
mJCw m=±l
1 p < J3r
m=
« m=
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 247
[<U)»](2a)«(2p,)«(2p,)i(2p,y
when they interact with each other to give some net effect. It turns out,
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
state of 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 num
L = h + h, h + U  1, h + h  2, . . .
, (h  l t)
. . . one uses S, P, D,
for individual electrons, to indicate L = 0, . . .
1, 2, ... For the present example with two p electrons one would
.
S = Si + s2 or S = Si — s2
and, since the spin quantum number has the fixed value of £, one can
have
S = 1 or S =
for a two outer electron system.
The energy of the electronic
state of an atom, with a given electron
configuration, dependent on the net electron spin. Exact calcu
is also
lations of the relative energies of states with different net spins cannot be
made. There is, however, a general rule formulated by Hund, which
applies both to atomic and molecular systems, that states with greater spin
lie at lower energies than those with smaller spin. Thus, for the two
outer electron example, 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, there
fore, 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 for the latter they may be parallel, i.e., S = 1.
turn of \/L(L + 1) (h/2w) for the electronic state of the atom. Further
more, s = \ implies an electronic spin angular momentum of i(h/2ir) on
the part of the individual electrons, and S implies a net spin angular
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 how the angular momentum con
tributions of the individual electrons could lead to net angular momenta
for the electronic state of the molecule. To combine the angular momen
tum contributions, convenient to introduce vectors and to deal with
it is
what is known as the vector model of the atom. The vector model assigns
an orbital angular momentum vector 1 to represent the magnitude
y/l{l + 1) (h/2w) and the direction of the orbital angular momentum
contribution that each of the electrons of the atom would make if the
electrons were noninteracting. Similarly, a vector L represents the
magnitude s/L(L + 1) (h/2ir) and the direction of the orbital angular
momentum of the atom when it is in the electronic state specified by L.
The possible values of the vector L are correctly given by the vector
combinations
The previous discussion has assumed that the orbital and spin
quantum numbers, and the corresponding angular momentum contribu
tions,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 INTRODUCTION TO MOLECULAR SPECTROSCOPY
"11
i — 2ir
i
*
L2*
ft
2?r
i
2
— JL
27T
PS
'2~
A.
2ir
L=0=
FIG. lOll The vector additions of the angular momentum vectors of two porbit elec
trons to give the total an angular momentum vector for the atom.
FIG. 1012 The vector diagrams that represent the ways in which the t and S vectors
can be combined to give resulting vectors.
J = 3S
s= 2 2JT
1—5.*.
,— 2 27T
L=2, L=2 L=2
,_3 *
= 1 fK L = 27
1
J
*'2
Since the numberways that the spin quantum number can be com
of
bined with the orbital angular momentum quantum number is often an
important feature (energy levels with a given value of L are sometimes
split into sublevels, depending on the coupling between L and S), we
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. The
initial effect 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,
but also the component of this along the internuclear axis. Thus,
although an orbit of the united atom is characterized by its total angular
momentum, as indicated by the quantum number I = 0, 1, 2, n . . . ,
FIG. 1013 Vector diagrams illustrating that three orientations can be taken up relative
On the left the simpler diagram based on vectors of length J(h/2ir) is shown. On the
right the correct diagram, with J[J + 1)(h/27r) vectors, is given. Either diagram shows
that the J = 1 state splits into three components.
M =1 2ir J = <
M=0
1 = .
M = l 2ir
27T
ELECTRONIC SPECTRA OF DIATOMIC MOLECULES 253
designate the quantum number for the component along the interhuclear
axis, and values of X = 0, 1, 2, are usually indicated by saying . . .
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
field of a diatomic molecule, the principal orbital angular momentum
feature is the component along the axis of the molecule, and the quantum
number for this is, therefore, designated by X.) With this notation the
step in the formation of a diatomic molecule from the united atom
initial
breaking apart a united atom. The notation based on angular momenta and the orien
tations of the orbitals are shown.
3dS
3d
3/J7T
3p
2p
2pir
JF""£
2p<r
2sa
*
254
U
United atom United atom
lsu
with
"deformed" nucleus
* Angular parts
of orbitals
O IB
3
isg
"I
Hi 6
o
?§§ o
111 a
a
o
b * N b
fcfcfci
S £
5 °
2 I
JE o
.E o
n
~^"^ "^h"^"'
O" o
Ik CO
256 INTRODUCTION TO MOLECULAR SPECTROSCOPY
FIG. 1016 A squarewell analogy to show the importance of the g and u character of
wave functions resulting from the uniting of two similar systems. Notice that the wave
function with the node goes to higher energy as the bond is formed while that without a
node goes to lower energy.
Infinite separation
Slight interaction
FIG. 1017 A correlation diagram describing the energies of the electron orbitals
of heteronuclear diatomic molecules. (From G. Herzberg, "Spectra of Diatomic Molecules,"
D. Van Nostrand Company, Inc., Princeton, N.J., 1950.) The vertical broken 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
FIG. 1018 A correlation diagram describing the energies of the electron orbitals of
homonuclear diatomic molecules. (From G. Herzberg, "Spectra of Diatomic Molecules,"
D. Van Nostrand Company, Inc., Princeton, N.J., 1950.)
UNITED
ATOMS
25?
ELECTRONIC SPECTRA OF DIATOMIC MOIECULES
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
labeled 1apA laps, 2wpA, and 2ttpb
, in Fig. 1017 and c c 2p, cr„2p, 7r u 2p, and jr„2p in
Fig. 1018,
Exercise 104. With the aid of Fig. 1018 suggest an electronic con
figuration for the molecule 2.
axis is, as for the atomic case, indicated by a superscript giving the
multiplicity of the state. If the molecule is homonuclear, the net
symmetry, i.e., the g or u property, is significant for the molecule as
well as for the individual orbitals. (The electronic state is even and
labeled with a g if the number of u electrons is even, and the state is odd
and labeled with a u if the number of. u electrons is 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)
FIG. 1020 The potentialenergy curves for various electronic states of the molecule Cj.
(From G Herzberg, "Spectra of Diatomic Molecules," D. Van Nostrand Company, Inc.,
Princeton, N.J., 1950.) (More recent data indicate that some revision is necessary.) The
symbol X is inserted to identify the ground state. The notation a, b, c, . . . and A, 8,
C, ... is added to identify the different states of the same multiplicity.
80,000 10
1
C( D) + C('S)
60,000
3
C( P) + C( \SJ
cr'oj + cr 'a)
£(cm )
3 1
40,000 C( P) + C( D) £(e.v.)
3 3
C( P) + C( P)
20,000
0
K10~ cm)
1
split into two or three lines, missing early members of the P, Q, and
R branches, and so forth.
For some diatomic molecules, a fairly complete analysis of the
ground and lower excited states can be made. For many more mole
cules, only a few of the observed bands can be definitely attributed to
specific electronic states. Much of the wealth of chemical bonding
information that has arisen from studies of electronic transitions is
PRINCIPAL REFERENCES
same as that of the ground state; formaldehyde and ethylene are, for
H
H:C::0:
where the placement of the dots represents the role of the outer electrons
in the molecule. With the advent of quantummechanical descriptions
based on the Schrddinger equation solutions for the hydrogenatom
problem, these diagrams could be refined to show in somewhat more
detail the spatial arrangement of the electrons. Thus, the diagrams
of the type used in the previous chapter, i.e.,
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 bond are said to be a orbitals,
and the bonding orbital resulting from the overlap of such orbitals is
known as a a bond. There will also be, as can be seen by inspection of
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 267
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 INTRODUCTION TO MOLECULAR SPECTROSCOPY
or simply
FIG. 111 Some spectroseopically important orbitals of H2CO and their symmetry
properties.
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 269
Exercise 111. Write the electronic configurations for the ground and
several excited states of the acetonitrile CH CN molecule.
3
CgB E c2 <r v
Ai 1 1 1 1 T.
A % 1 1 1 1
Bi 1 1 1 1 Tx
B 2 1 1 1 1 Ty
270 INTRODUCTION TO MOLECULAR SPECTROSCOPY
TABLE 1 12 The Effect of Symmetry Operations on <p(1). Presumed to Be of the Type A it
and <p(2), of the Type B u and on the Product ^(1)^(2)
C,
where <p(l) is the wave function for the orbital occupied by electron 1,
displayed, can then be easily deduced from the symmetries of the singly
occupied orbitals. The results are shown in Table 113.
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 271
=
Mx JVex»it«dM*f ground dr
Kl = J^MiitodftdrVoimd A"
or
M* = MsTcitodM^ground *"
FIG. 112 A schematic diagram for the ultraviolet absorption spectrum of a carbonyl
compound.
a
S
a i
«
E
a
£
§
1
1 1
1,500 2,000 2,500 3,000 3,500 4,000
X in A
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 273
TABLE 114 The Ultraviolet Absorption Bands of Carbonyl Compounds and Suggested
Assignments
(Values of X and / are Typical Values for a Number of Compounds)
Assignment
"band max /
(A) (osc. strength) Configuration Upper state
change symmetry
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 and important aspect of electronic transitions that
has not been considered but which is pertinent to a discussion of local
ized absorbing groups, and to the conjugated and aromatic systems that
will be dealt with in the final section of this chapter, is the process by
which molecules in excited electronic states lose their excess energy and
revert to groundstate molecules. This process, as we will see, can
involve fluorescence and phosphorescence emission of radiation.
(It should be mentioned that, since the symbols for electronic
states do not immediately reveal the relative energies of the states, it is
often the case, both absorption and emission spectra are dealt with,
designations according to this system avoid much of the confusion that
can However, when the transition is discussed in terms of the
arise.
of the 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.)
Exercise 1 1 3. Draw the tt and it* orbitals of ethylene, and assign them
to 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?
FIG. 113 The bonding and structure of octatetraene. Each carbon atom forms three
<r bands, Indicated by —
with fp' hybrid orbitals.
, Each remaining 2p orbital, shown os
an atomic orbital here, enters into trie delocalized x bonding.
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 277
I = A sin — n = 1, 2, 3, . . . (2)
e (3)
" 8ma*
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
46
_ £4 = (52 .4>) ^
8
(4)
with a = 9.5 A, to be
v = 27,000 cm 1
(5)
Sec. 46, the intensity with which a sample absorbs radiation can be
calculated. The prediction, for octatetraene, that the integrated absorp
tion coefficient be, according to Eq. (58) in Chap. 4,
32iVe !!
aV
3ir/icl,000
= 1.9 X 10 19 sec 1 cm 1 mole" 1
liter (6)
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 con
sisting of all double bonds alternating with single bonds. It is responsible
for the red color of tomatoes. Calculate the wavelength expected for
ELECTRONIC SPECTRA OF POIYATOMIC MOLECULES 279
the w—* v* transition and compare with the observed band maximum
which occurs at X = 4,700 A.
of the molecular orbitals and the electronic states will be brought out,
and it will be shown that some assignments of observed absorption bands
to the states involved in the transitions can be made. 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
these atomic orbitals can be combined to provide suitable molecular
orbitals. The guiding principle here is that an electronic wave function,
or molecular orbital, of the benzene molecule must conform to the
symmetry That is, by an argument analogous to that
of the molecule.
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
of the irreducible representations of the group. Let us now see if such
molecular orbitals can be obtained by suitable combinations of the six
2prr atomic orbitals.
D, E 2C e 2C1 C 3
3C 2 3c;
A, I I 1 i
A, I 1 1 i T,
B, 1 —1 1 I i
B2 X 1 1 1 i
Bi 2 1 2 T*,T y
E, 2 —1 —1 2
The point group to which the nuclear skeleton of the benzene mole
cule belongs is D The treatment can be somewhat simplified if the
6fi .
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
problem can be analyzed in terms of the simpler
simplification, the
point group D
which the character table is given in Table 115
8, for
and the symmetry elements are illustrated in Fig. 116.
The six 2px atomic orbitals form a basis for a reducible representa
tion of the group, i.e., the transformation matrices that are obtained
when the various symmetry operations are applied to these atomic
orbitals will lead to representation matrices that can later be reduced.
Thus to obtain the reducible representation, one investigates the oper
ations on the individual s orbitals and writes the transformation equations
FIG. 1 1 6 The symmetry elements of the Da point group. Note that, unlike the ease for
the Dbi point group, symmetry with regard to the plane of the molecule is not considered.
Cfin C gT Cj
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 281
as
p' p"
/l 0^
E =(010000 character for E = 6
^000100^
10 character for d —
and so forth. In this way one finds that the character of the reducible
representation corresponding to the six 2pir orbitals is
= A l +B +E +E
l l t (8)
We see from this that the atomic orbitals should be combined to give
molecular orbitals, one of which transforms according to the symmetry
type A 1, one according to Bh one pair according to the degenerate class
Ei, and another pair according to E 2 We must now see what combina .
* 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
molecules. Capital letters are reserved for the symmetry type and the net electronic
state of an atom or molecule.
in various ways, 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
functions as in Fig. 117. One should recognize that a corresponding
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.
The order of the energies of these individual molecular orbitals
can be recognized by recalling that, as can readily be seen from the
particleinabox problem, the more nodes there are in a wave function,
the higher is its energy. The wave functions of Fig. 117 have been
ordered so that the a,i function at the bottom of the diagram has the
lowest energy and the &i function at the top has the highest energy.
Calculations of the energies of these orbitals can be made, and the
simplest calculation leads to the spacing shown in Fig. 118. These
energy spacings are usually expressed in terms of a quantity which
represents an integral that is difficult to evaluate.
The symmetry designations for the orbitals on the basis of the
De» point group, for which the character table is given in Table 117,
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 accordance with the De
group.
ei(e iu )
Cl("«l B J
a, <ai«)
w 1
z»
XJS la *
XB«. 1 4 4 01
Now, unlike the situation encountered with nondegenerate representa
tions, a reducible representation is obtained. It is necessary to analyze
Alg 1 1
A iu 1 1
At, 1 1 —1 _1 _J j
Aiu 1 1 —1 —1 —I —I i i
T,
Bi„ 1 —1 1 —I _1 J i
Biu 1 —1 1 _1 I J i
Bt a 1 —1 1 _1 _1 I i
Bi„ 1 —1 1 —1 —I _1 „1
Ela 2 —1 2 2 _1 2
E lu 2 —1 2 2 —i 2 T T
Eig 2 1 1 2 2 —1 —i 2
Eju 2 —1 —1 2 2 2
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 285
to have both singlet and triplet states, and as suggested by Hund's rule
cited previously, calculations indicated that the triplet states lie 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 Excitedstate
configuration configuration
286 INTRODUCTION TO MOLECULAR SPECTROSCOPY
Table 117 that, for a D 6h molecule, transitions to the states with sym
metries ij, and E lu would be allowed. Furthermore, changes in multi
plicity are expected to be forbidden, and one expects only singletsinglet
transitions to lead to strong absorption bands. Thus the jnost intense
band in the absorption spectrum of benzene should be assigned to the
completely allowed transition to the 1
E Xu state.
The absorption spectrum of benzene shows, however, more absorp
tion bands than the single most intense band that is assigned to the
l
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 The absorption spectrum of benzene in the ultraviolet spectral region. (From
K. S. Pitzer, "Quantum Chemistry," PrenticeHall, Inc., Englewood Cliffs, N.J., 1953.)
5r
\B ta or %,  'A,,
Rydberg series
1
3
1,500 2.000 2,500 3,000 3,500
X in A
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 287
been suggested that the band near 2,100 A is due to either the transition
lB^i—iAig or 1 E ig <^ 1 A u These forbidden transitions could occur
.
H H H H
\c— / \c=c/
II 
c—
II I I
c=c
H
/. \H H
/ \H
in a similar manner to that in which benzene was treated above.
288
INTRODUCTION TO MOLECULAR SPECTROSCOPY
simplest form, which is all that will be introduced here, the theory
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
exert on the d electrons of the metal ion. (The coordination compound
is pictured as being held together primarily by the attractive interaction
of the charge of the metal ion with the charges or dipoles of the ligands.)
equivalent, such ions have the symmetry of the point group O*. The
character table for this group is given as Table 118, and some of the
Ai, 1 1 1 1 1 1 1 1
A lu 1 1 1 1 1 1 —1 1 1
A ig 1 1 1 1 1 1 1 1
Azu 1 1 1 1 1 1 —1 1 1
E, 2 —1 2 2 —1 2
Eu 2 —1 2 2 2
Tu 3 i 1 1 3 1 1 1
Ti u 3 l 1 1 3 1 1 1 J X) 1 yi i z
Tn 3 l 1 1 3 1 1 1
Tzu 3 l 1 1 3 1 1 1
290 INTRODUCTION TO MOLECULAR SPECTROSCOPY
FIG. 1 111 (a) The geometry of an octahedral complex. All six ligonds are equivalent,
and the complex belongs to the symmetry point group O;.. (b) Some representative
symmetry elements of the Oj, point group.
NH.
^
c 4 .c;
*T NH.
(a)
to Cj and C 4
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 291
group O
can be recognized as containing the doubly degenerate irre
h
One must, however, keep in mind that no unique and that the axis is
3£
2.")
d <*i ¥ z>
d („2_ z Z)
292 INTRODUCTION TO MOLECULAR SPECTROSCOPY
FIG. 1113 The removal of d orbital degeneracy by an octahedral field. The extent of
splitting is customarily discussed either in terms of A or lODq. Both notations are included
here. .
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 293
and (e,) 1
. Since there is only one electron, the electronic states are
similarly described and are labeled with the capital letter designations
T ig and E„. Furthermore, as for the original 2
D atomic state, one
indicates the spin and writes the two states as 2 T 2„ 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
,
2
^» <— 2
?V
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 .
294 INTRODUCTION TO MOLECULAR SPECTROSCOPY
tively we can say that for [Ti(H 2 0)e] 3+ the value of the crystalfield
Now let us consider the situation when there are two d electrons.
1
FIG. 1114 The energylevel diagram for a metal ion with one d electron, i.e., d con
figuration, showing the effect of increasing crystal field effect. The energy scale is
arbitrarily assigned the value zero for the ground state of the undisturbed ion. The posi
1
tion of [Ti(OHj) 6]
3+ is located and the value A determined by the frequency of 20,400 cm
of the observed absorption band.
[Ti<OH 2 ) 6 P
State 'E g
configuration (e„)
State 'T^
1
configuration (t 2g )
Large
Zero
crystal field
crystal field
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 295
pattern of these states is not easily predicted but can be determined from
analyses of atomic spectra. In this way the pattern at the origin of Fig.
1115 can be drawn for the V 3+ ion.
Let us now move over to the far righthand side of the diagram
and consider the states that would be expected for a d 2 ion subjected
to a strong crystal field. The three possible electronic configurations
that must be considered are, in order of increasing energy, (t 2g )
2
, (k g ) 1 (e g ) 1 ,
and (e„) 2
. Now, to find what electronic states these configurations cor
respond to we must, as in the previous treatments of localized groups
and conjugated systems, form the direct product of the representations
of each electron in a given configuration. Analysis of the (<2»)
2
configura
tion is illustrated in Table 119. In a similar way the states for the other
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 of the Determination of the Electronic States Arising from the
Configuration (hg)*
Oh E Ct C\ Se
XT,, 3 1 1 1 3 1 1 1
XT,, X XT,, 9 1 1 1 9 1 1 1
XAjg 1 1 1 1 1 1 1 1 1 1
XB, 2 1 2 2 1 2
XT la 3 1 1 1 3 1 1 1
XT,, 3 1 1 1 3 1 1 1
XA U + XB, + XT U
+ XT,, = 9 1 1 1 9 1 1 1
296 INTRODUCTION TO MOLECULAR SPECTROSCOPY
TABLE 1110 Electronic States Arising from an Electron System Subject to Octahedral
Symmetry
Electronic configuration
Electronic states
Ion subject to octa
Free ion
hedral symmetry
d\ d 8
WW
2
(«») »A,„, 'Ai,, >£,.
T„. 3 T 2o ,
ir.», T„
(U* Ti,, 'Aip, >£„ T,,
d\d? (e») 3 2
£„
fol'fe)'.
4
r s «, 2 2 r l0 2«r l( , ,
(<i.)
,
(«.)
1
«?,„, *T i0 *A ln M,», 2T,,,
, 2T„
(*i»)* <A 2 „, »£„, *T 1( «T„ ,,
(WW *£„,
2T
3
A l5 »A 2o 23£„, 2»r lln 2»r 8 „' 'A,,, >A,„, >£„,
„ 2T
, ,
1( 2„
d« (WW s
r 28
(WW T l0 , *T U , M„, A 2o 2^ 2'7 2
, , 1( , ) 2*T 2 „
(WW •r,„,
4T,„
*r lln
4»r,„
M,„ 2^„, *T lg *T lg , , 2'A lg , *A 2 „, VE B,
are given in Table 1 110. (We will see later that the configurations and
10 "
states for d n systems are similar to those for d systems.) Again, it is
FIG. 1115 A schematic correlation diagram for the states of a d2 ion. On the left is the
energylevel pattern for the free ion; on the right is the pattern for very strong crystal
fields. The correlation lines are drawn with regard to the multiplicities of the levels and
the correlations of Table 1111.
Free ion
Strong \3™
crystal field '»
(No repulsions between
the two d electrons)
298 INTRODUCTION TO MOLECULAR SPECTROSCOPY
by joining up the appropriate states of the right and left sides of Fig.
1114.
The way in which such correlations must be made was first shown by
H. Bethe [Ann. Phys., 57: 3, 133 (1929)] by means of a grouptheoretical
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 appropriate to point out that the often used spectroscopic
trick of recognizing that the treatment for an atom with two d electrons,
i.e., a d system, is in many respects identical to that for an atom lacking
2
Ni++, which has the configuration d has a set of atomic states arranged
s
,
S Alg
P Tu
D Ea + T H
F A 2a + Ti, + T 2g
G A le +Ea + T lg + T lg
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 299
FIG. 1116 The schematic correlation diagram between the free ion and the strong
octahedral field complex for d8 ions.
Free ion
Strong
crystal field
(No repulsions between
the d electrons)
300 INTRODUCTION TO MOLECULAR SPECTROSCOPY
Exercise 1111. What are the differences in the limit of strong crystal
fields of the energies of the configurations {h Y, (hgYieg) 1 {t2.g) l {e g y, and ,
(e g )
3
Illustrate the answer by an energy diagram and show the energy
.
FIG. 1117 The energylevel diagram for a d 8 ion, such as Ni ++, in a field of octahedral
symmetry. The energies of the important states with the same multiplicity as the ground
""
state are shown as heavy lines. The position of [NilHjOle]" 1 1
is located along the abscissa
to fit the observed spectrum. (From 1. £. Orge/, "An Introduction to Transition Metal
Chemistry, "Methuen & Co., Ltd., London, 1960.)
(Ni(H 2 0) 6 ] « 2! /<V4
(A = 8,500 cm" ')
20,000
10,000
E
u
c
i
 10,000
20,000
««,) <v
5,000 15,000
ELECTRONIC SPECTRA OF POLYATOMIC MOLECULES 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. Further
of the other triplet states, the
more, consideration of the transitionmoment integral leads to the con
clusion, well known in atomic spectra and referred to as the Laporte rule,
that no transitions between states arising from a given configuration
such as d 2 are allowed. This is based on the symmetry result that, as
Fig. 1112 shows,d orbitals are symmetric with respect to their
all
"Wm^ = ylog
( j ) =5 cm1 mole 1 liter (10)
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 man
ganese 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 complexes have led
to the suggestion that a value of A of about 7,800 cm" 1
for [Mn(H 2 0) 6 ++ ] ,
FIG. 1118 The absorption spectrum due to the octahedral ion [Ni(H 2 0)6] ++. [From
Holmes and McClure, J. Chem. Phys., 26: 1686 (1957).]
50,000
<"V<V
FIG. 1119 The energylevel diagram for a a* 5 ion such as Mn" "" ". Only the ground
1 1
state, designated as 6 S and e T ig and quartet states are shown. (From L. E. Orgel, "An
,
XinA
6,000 5,000 4,000 3,500
1 1 i i
0.03
0.02
An
FIG. 1120 The absorption spec
trum due to the ion [Mn(H 2 0) 6 ] ++ .
[From C. K. Jorgensen, Acta. Chem.
Scand., 8: 1502 (1954).]
0.01
A^ 20,000
1
25,000
><(cm _1 )
30,000
304 INTRODUCTION TO MOLECULAR SPECTROSCOPY