6.

1 Vibrational Modes and Their Symmetries 165

and particularly if its symmetry declines, many of these vibrations have very
CHAPTER 6 similar frequencies and are no longer individually distinguishable. At this
level, spectroscopic assignment is usually confined to identifying frequencies
associated primarily with specific chemical structures (e.g., functional groups).
We will, therefore, confine our discussions to smaller molecules, where the
Vibrational Spectroscopy power of symmetry and group theory is greatest. These are also the kinds of
molecules for which detailed force constant determinations are most tractable,
although we will not consider such calculations in this text.

Theoretical chemists were aware of the power of group theory to handle prob-
lems in quantum mechanics as early as the late 1920s through the work of sci- 6.1 Vibrational Modes and Their Symmetries
entists such as Herman Weyl,* but most experimentalists had little need and
even less interest in the subject. This changed after World War II with the de- The individuaI atoms of a molecule are constantly in motion over the enti re
velopment of commerciaI Raman spectrometers and most especially infrared range of real temperatures above absolute zero. These individuaI atomic rno-
spectrophotometers. Soon infrared spectroscopy became a standard laboratory tions result in three kinds of molecular motions: vibration, translation, and ro-
procedure, and with this grew a need to understand the theoretical underpin- tation. To illustrate, we will first consider the simplest of molecules, a di-
nings of the technique. Two texts from the post-war period dealing with vibra- atomi c molecule AB.
tional spectroscopy, which remain standard references today, are probably more First, suppose the A and B atoms move apart from their equilibrium in-
responsible than any others for making chemists in generaI aware of the ap- ternuclear distance, re (Fig. 6.la), so as to stretch the chemical bond (Fig.
plicability of symmetry and group theory to practical problems of the experi- 6.1b). As they move apart, away from the equilibrium position, they will ex-
rnentalist. The first of these, Gerhard Herzberg's 1945 work lnfrared and Raman perience a restoring force, F, in opposition to the motion. If we assume that
Spectra of Polyatomic Molecules, t contains spectroscopic data and assignments the molecule follows classica l mechanics, the restoring force will be propor-
for nearly ali simple compounds studied prior to its publication. Moreover, it in- tional to the displacement from the equilibrium distance, 8.r, and vary ac-
'I troduced chemists to symmetry arguments, group theory techniques, and force cording to Hooke's law:
i. constant calculations, while establishing the notation and nomenclature for the F = - k Sr (6.1)
spectra of polyatomic molecules that has become standard today. Following
Herzberg's book by a decade, Wilson, Decius, and Cross' Molecular Vibrationsi where k is the force constant. At some point the restoring force will cause the
introduced many chemists to rnatrix techniques for carrying out force constant two atoms momentarily to arrest their travel away from each other, after
calculations and furthered understanding of the applicability of symmetry and which they will reverse their motions and begin to travel toward each other.
group theory methods, including analyzing spectra of related cornpounds As they approach one another they will pass through the equilibrium internu-
through group-subgroup relationships. As a result, many chemists who received clear distance and continue to move together, until their mutuai repulsions ar-
their training after publication of these works first encountered symmetry and rest them at a minimum separation (Fig. 6.1c) and drive them back in the op-
group theory in connection with their application to vibrational spectroscopy.
As with other applications of symmetry and group theory, these tech-
niques reach their greatest utility when applied to the analysis of relatively (a) At equilibrium
srnall molecules in either the gas or liquid phases. In such cases, the observed
spectroscopic frequencies can be assigned to specific vibrational motions in-
volving all the atoms in the molecule. As the size of the molecule increases,
~ (b) Strelehed
*Weyl's c1assic 1928 work Gruppentheorie und Quontenmechanik is available as a reprint of the
1931 English translation, Group Theory and Quanturn Mech anics, Dover Publications, New
1< Te
,I < Ar
,I
York,1950.
j G. Herzberg, Molecular Speara and Molecular Structure. Il. Infrared and Raman Spectra of
!Polyalomic Molecules, Van Nostrand, Princeton, NJ. 1945. A corrected reprint edition of this
book has been published by Krieger Publishers, Melbourne, FL.
(c) Contraeted
tE. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations: The Theory of Infrared
and Raman Vibrational Spectra, McGraw-Hill, New York, 1955. A paperback reprint of this book Figure 6_1 Motions of a harmonic
has been published by Dover Publications, New York. oscillator, AB.
166 Chapter 6 Vibrational Spectroscopy 6.1 Vibrational Modes and Their Symmetries 167

posite direction. This periodic series of motions constitutes one cycle of the vi-
brational mode of the molecule as a harmonic osciLLator.If the molecule were
v = 5, E5 = (l1/2lhv
to obey classica l mechanics, the potential energy of the system throughout the
vibrational cycle would vary parabolically as a function of displacement: v = 4, E4 = (9/2lhv

(6.2) v = 3, E3 = (7/2)hv
~
However, unlike a classica l mechanical systern, the energy of a real vibrating Q)

c v = 2, E2 = (5/2)hv
w
molecule is subject to quantum mechanical restrictions. As such, the oscil1at-
v = l, Ej = (3/2lhv
ing molecule can assume only certain values of vibrational energy. From the
Schrodinger equation for a harmonic oscillator, the allowed energy levels are v = O, EO = (l/2)hv
given by
1 Zero-point energy
E(v) = hlJ(v + 2) (6.3)
ClrH
where v is the vibrational quantum number, whose values may be v = 0, 1,2, ... ; Internuclear separation
u is the vibrational frequency in Hertz; and h is Planck's constant. By long- Figure 6.2 Energy levels of a harmonic oscillator.
standing practice , vibrational spectroscopists usually quote frequencies in
units of cm -1, called wavenumbers, defined as il = Il À, where À is the wave- where f.L is the reduced mass given by f.L = mAmB/(mA + mB), in which m»:
length in centimeters.* In keeping with this, it is more convenient to define and mB are the masses of the individuai atoms. Note that lJ does not depend
the energy of the system in wavenumber units, called term values, T The term on the value of the quantum number V. In other words, the molecule's vibra-
value is defined as T = Elhc, where c is the speed of light in vacuo in cm·s-1. tional frequency is the same in all states, even though the energy E (or 1)
Thus, Eq. (6.3) becomes changes with v [Eq. (6.3)].
T(v) = ii(v + t) (6.4)
The basic quantum mechanical selection rule for a harmonic oscillator
limits changes in vibrational energy to transitions between adjacent states;
that is, Llv = :!: 1. Applying Eq. (6.4) to any two states v and v + l, we see
Equation (6.4) suggests a model in which we have a series of equally
that the energy separation between successive levels is LlT = ii. In other
spaced energy levels, as shown in Fig. 6.2. The minimum energy of the sy~-
words, for a harmonic oscillator the energy of the transition in wavenumbers
tem, called the vibrational ground state, is attained when v = O. Note that it
is the same as the molecule's vibrational frequency, ii.
does not lie at the minimum of the parabola defined for the classical oscilla-
Real molecules are not perfect harrnonic oscillators. The variation of the
tor [Eq. (6.2)]. The classical minimum refers to the hypothetical condition of
potential energy of the system with internuclear separation usually is not a
a quiescent molecule with its atoms at the equilibrium internuclear separa-
symmetric parabola, but rather tends to have the skewed appearance of a
tion. The difference between this hypothetical minimum and the actual min-
Morse curve, as shown in Fig. 6.3. This kind of potential energy dependence
imum energy of a vibrating molecule in its ground state (v = O) is called the
describes the behavior of an anharmonic oscillator. By solving the Schrodinger
zero point energy. Notice that for increasing values of v and corresponding
equation for the Morse potential, energy states for the anharmonic oscillator
higher values of vibrational energy the internuclear separation becomes
as term values are given by the equation
greater at the extreme stretch and less at the extreme compression of the vi-
bration, Hence, increasing vibrational energy occurs with higher vibrational
amplitude. The vibrational frequency of the harmonic oscillator in any state
T(v) = ii(v + t)'::: iixe(v + tf + ... (6.6)

is related to the force constant by where Xe is the anharmonicity constant. The higher terms in Eq. (6.6) afe
usually small and are routinely omitted. The separation between any two
v = 2~ J(~) (6.5) successive energy states, then, is given by
LlT = ii - 2xeii (v + 1) (Llv = ± l) (6.7)
*Striclly speaking, wavenumbers (cm-l) are not frequency units, but rather reciproca I wave-
length units. However, Il = cl); = ev, where e is the speed of light in vacuo, so wavenumbers are where v is taken as the value of the vibrational quantum number for the lower
directly proportional lo frequency. Thus. "wavenumber" is routinely used as if it were a fre- energy state. With rare exceptions, Xe is a positive number, so the separation
quency unito between succes ive states becomes progressively srnaller as v increases.
 168 Chapter 6 Vibrational Spectroscopy
6.1 Vibrational Modes and Their Symmetries 169

monicity is usually ignored in routine work. Ignoring anhannonicity in these

cases is often more a practical matter, since including quantitative allowances
for it would acld an extreme level of complication to the analysis of the spec-
tra. Thus, to a certain elegree of approximation, the spectroscopically ob-
serveel frequencies for most polyatomic molecules are routinely taken as
equal to the molecular vibrational frequencies.v
We have taken some care here to elescribe the atomic motions leading to
c-,
DO
(;;
vibration, because these are the kincls of motions that can be elirect1y mea-
c:
W sured with infrared and Raman spectroscopy. However, the atoms of a eli-
v=3 atomic molecule also can move in ways that are not vibrational. Suppose both
v =2
A and B move in parallel in the sa me direction, resulting in a translation of
v = l
the entire molecule through space. This is not a perioelic motion, so it has no
interaction with electromagnetic raeliation; that is, it cannot be eletecteel by
infrareel or Raman spectroscopy. Since any motion in space can be resolveel
into projections along x, y, and z of a Cartesian coordinate system, we can see
that for every molecule there must exist three translations, Tn Ty, and T,
Internuclear distance
(Fig. 6.4). Similar1y, suppose A and B move in opposi te directions perpen-
Figure 6.3 Energy levels of an anharrnonic oscillator (Morse potential curve). Note
dicular to the bond axis. This will cause the molecule to tumble or rotate.
the successively smaller separations between energy states as v increases (bottom to
Unlike translation, rotation can be detecteel spectroscopicaUy, because it oc-
top )~
curs with a repeating periodic cycle. However, the frequencies of rotations lie
The frequency recorded for a molecular vibration by infrared or Raman in the microwave region and are not directly observeel in the frequency range
spectroscopy corresponels to the energy elifference between two vibrational of most vibrational spectroscopy.' From the standpoint of vibrational analy-
states. A transition between the state v = O and the state v = 1 defines a vi- sis, rotations constitute a nonvibrational oscillation. For a eliatomic molecule,
brational fundamental. Infrareel absorption involves exciting a molecule from
a lower vibrational state, usually the grounel state v = O, to a higher state for
which v > 0.* For a funelamental, then, this transition is v = O --7 V = 1. With
Raman scattering, ilv = + 1 for the Stokes funelamentals (v = O --7 V = 1) and
~v = - 1 for the anti-Stokes funelamentals (v = 1 --7 V = O). However, in
most Raman work, only the Stokes frequencies are sought, since they are sig-
nificantly more intense. Thus, in most cases the observeel spectroscopic fre-
quency of the funelamental corresponels to a vibrational transition for which
ilv = + 1. This frequency, expressed in wavenumbers (cm-l), is ilT in Eq. Figure 6.4 Movement of A and B
(6.7). By this, taking v = O,we can see that the spectroscopically observed fre- atoms resulting in translations of the
quency for a fundamental is il T = D - 2xe D.This frequency will more closely molecule AB.
approximate the rnolecular vibrational frequency, D, when the anharmonicity,
"The effects of anharmonicity in the vibrations of polyatomic molecules become apparent in the
Xe, is extremely smal!. At the limi t of a true harmonic oscillator (x, = O), the
spectroscopic frequencies of overtones and cornbinations, as discussed in Section 6.5.
observed spectroscopic frequency is the same as the molecule's vibrational tWith samples in the gas phase, the presence of quantized rotational states can often be seen as
frequency. However, for many real dia tomi c molecules, the anharmonicity is bands of fine structure (P and R branches in the infrared spectrum; O and Sbranches in the
appreciable and causes a significant difference between the spectroscopically Raman spectrum) on both sides of the frequency for the pure vibration (Q branch). They can
also be observed directly in the Raman spectrum as very low frequency bands on both sides
observed frequency and the molecule's vibrational frequency. Looking ahead
(Stokes and anti-Stokes) of the exciting frequency (Rayleigh line). In many cases the Q branch,
to polyatomic molecules, with which we will be primarily concerneel, anhar- for the vibration without rotation, is not spectroscopically observable, being forbidden on the ba-
sis of quantum mechanical considerations. Further detail of the theory of vibrational-rotational
! "For most molecules at room temperature the thermal distribution of energies highly Iavors the
spectra, which is covered in most physical chemistry texts, is not essential to the purposes of this
ground vibrational state. For example, [or H J5C1 at room temperature it can be shown that the
chapter. See, for example, P Atkins, Physicol Chemistry, 5th ed., W. H. Freeman, New York,
fraction of the molecular population with v = 1 to that with v = O is 8.9 X 10-7• Thus, virtually
1994, Chapter 16.
ali molecules are in the vibrational ground state.
170 Chapter 6 Vibrational Spectroscopy 6.1 Vibrational Modes and Their Symmetries 171

we can define rotational motions about the x and y axes (designated Rx and the three directions of a Cartesian coordinate system. Therefore, any mole-
Ry), but we cannot define such motion about the z axis (the bond axis), as cute composed of n atoms possesses 3n degrees offreedom of motion. As with
shown in Fig. 6.5. Spinning about the z axis does not cause the mole cui e it- diatomic molecules, these 3n degrees of freedom include vibrations, transla-
self to move. Looking beyond the diatomic case, we can see that this is true tions, and rotations. The vibrational motions of the atoms can always be re-
for any linear molecule, regardless of the number of atoms composing it. solved into fundamental vibrational motions for the entire molecule, called
However, for a nonlinear molecule the rotation about z does cause the mol- normal modes of vibration. The number of these norrnal modes will be 3n mi-
ecule to tumble (cf. Fig. 6.6a,b). Thus, for all nonlinear molecules there are nus the number of nonvibrational motions (i.e., translations and rotations).
three rotations, R<, Ry, and RI.' As we have seen, a linear molecule has three translations and two rotations.
Let us now consider the motions of a polyatomic molecule composed of Subtracting these from the 3n degrees of freedom, we see that a linear mole-
n atoms. The motions of each atom can be resolved into components along cute possesses 3n - 5 vibrational modes. A nonlinear molecule has three
translations and three rotations. Therefore, a nonlinear molecule possesses
3/1 - 6 normal modes. Like the diatomic case, each normal mode of vibration
has a characteristic frequency and can assume a series of quantized energies.
The frequencies recorded by infrared and Raman spectroscopy arise from
transitions between these states. A transition of the type v = O -7 V = 1 de-
fines a fundamental of the normal mode.
. Although we ha ve seen why a linear molecule has one less rotation than
a nonlinear molecule, you may be wondering how this necessarily implies that
a linear molecule has one more vibrational mode than a nonlinear one with
the same number of atoms. The answer is that one of the rotational modes of
a nonlinear molecule becomes a bending vibrational mode when the mole-
cule is made linear. This is most easily seen for a triatomic molecule, as shown

-D- z
Figure 6.5 Rotations of a diatomic
in Fig. 6.7.
Relative to the overal! molecular symmetry, al! of the 3rt degrees of free-
molecule. dom-normal modes of vibration, translations, and rotations-have symme-

-+.
No rnolecutar rotation
try relationships consistent with the irreducible representations (species) of
the molecule's point group. In other words, we can catalogue all degrees of
freedom according to the appropria te Mulliken symbols far their corre-
(al sponding irreducible representations. To do this we locate a set of three vec-
tors along Cartesian coordinates at each atom, representing the three degrees
of freedom of that atomo We then make the entire set of 3n vectors a basis
Rx
for a representation in the molecule's point group. The reducible representa-

(bl
-A. Rx
----;""-::rr'kb~A....L.."""":;-'7=:::_-O
(!f"
+
~ +
Rotation

+ +
! becomes

Figure 6.7 Ooe rotation of a

nonlinear triatomic molecule be-
Figure 6.6 Rotations of (a) a linear molecule and (b) a nonlinear molecule. A non- bending vibration comes a beoding vibrational mode
staodard axis choice has been made for the nonlinear molecule to facilitate comparisoo. + + if the molecule is made linear.
172 Chapter 6 Vibrational Spectroscopy 6.1 Vibrationai Modes and Their Symmetries 173

tion is then reduced into its component irreducible representations, which O O O O O O -1 O O -X3

correspond to the symmetries of the 3n degrees of freedom. The symmetries O O O O O O O -1 O -13

of the translations and rotations can be identified from the character table O O O O O O O O 1 Z3
from the listed transformation properties for unit vectors and rotational vec- O O O -1 O O O O O -X2

tors, respectively. These are subtracted from the collection of symmetry O O O O -1 O O O O -Y2 (6.9)
species cornprising the overall reducible representation, leaving the collection O O O O O 1 O O O Z2
of Mulliken symbols for the 3n - 6 normal modes (3n - 5 normal modes for -1 O O O O O O O O -XI

linear molecules). O -1 O O O O O O O -YI

To illustrate, consider the bent molecule S02 (C2v). Figure 6.8 shows the O O 1 O O O O O O ZI
vector basis for the reducible representation of the 3n degrees of freedom,
[3n' We will need 9 x 9 transformation rnatrices to show the effects of the op- This gives a character of -1 for the C2 operation. Note that only the centraI
erations of C2v on the nine individuai vectors. By extrapolation, we. can see 3 X 3 block matrix, associated with the vector transformations of the non-
that for any molecule we would need 3n X 3n matrices. Clearly, carrying out shifted S atom, contributes to the overall character of the full 9 X 9 matrix.
this kind of mathematical work even for srnall molecules would be cumber- The a(xz) operation exchanges the two oxygen atoms and reverses the
some, so we willlook for shortcuts to the full-matrix approach as we proceed
sense of all Y vectors. In full-matrix notation this is
with this example.
For S02, the identity operation, E, leaves ali vectors in piace. In full-
matrix notation this is O O O O O O 1 O O XI X3

O O O O O O O -1 O YI -Y3

O O O O O O O O 1 ZI Z3
1 O O O O O O O O Xl
O O O 1 O O O O O Xz X2
O 1 O O O O O O O Yl O O O O -1 O O O O (6.10)
O O 1 O O O O O O ZI
O O O O O 1 O O O
O O O 1 O O O O O X2
1 O O O O O O O O
O O O O 1 O O O O Y2 (6.8) O -1 O O O O O O O
O O O O O 1 O O O Z2
O 1 O O O O O O
O
O O O O O O 1 O O X3
O O O O O O O 1 O
O O O O O O O O 1 This gives a character of 1 for the a(xz) operation. Again, only the centrai
3 X 3 block matrix for the nonshifted S atom contributes to the character.
Finally, the a(yz) operation leaves all atoms in piace but reverses the
From the trace of the transformation matrix we obtain a character, XE, of 9,
sense of ali X vectors. In full-matrix notation this is
which is the value of 3n for S02' We can see from this that for any molecule
of n atoms it must be that XE = 3n.
The C2 rotation exchanges the two oxygen atoms and reverses the sense -1 O O O O O O O O
of ali X and y vectors. In full-matrix notation this is O 1 O O O O O O O YI
O O 1 O O O O O O Zl
O O O -1 O 0-- O O O -Xz

O O O O 1 O O O O Y2 (6.11 )
O O O O O 1 O O O 'Z2

O O O O O O -1 O O -X3

O O O O O O O 1 O 13
O O O O O O O O 1 Z3

This gives a character of 3 for the a(yz) operation. Here, all atoms remain
Figure 6.8 Orientations of vectors for S02 lo form the basis for a representation of nonshifted, and ali their associated 3 X 3 matrices contribute to the overall
the 3rt degrees of freedom. The rnolecule Iies in the yz plane. character.
174 Chapter 6 Vibrational Spectroscopy 6.1 Vibrational Modes and Their Symmetries 175

We see from Eqs. (6.8) through (6.11) that each 9 x 9 operator matrix species (e.g., (x, y) in D4h, and (x, y, z) in Td), use the listed character for that
contains three 3 x 3 block operation matrices, one for each atomo For any op- species as the contributions of the associated vectors for each operation. To
eration Ri, alI the individual-atorn operator matrices (3 X 3 matrices) ha ve illustrate, for C2v Z transforms as A h X transforms as B1, and y transforms as
identicai form and therefore have the same character, Xi' Only individual-atorn B2. Using the characters from these three species we obtain the following val-
block matrices that lie along the diagonal of the fulI operator matrix contribute ues of Xi for the four operations of the group:
to the overall character for the operation, XR' Moreover, we see that only those C2v E C2 O'(xz) u(yz)
3 X 3 block matrices for atoms that are not shifted by the operation contribute
to the character of the overall matrix. Thus, to find XIò the character [or the AI 1 1 1 1 Z

overall operation, count the number of atoms that remain nonshifted by the op- BI 1 -1 1 -) x
eration, N;, and multiply by the contribution per nonshifted atom, Xi; that is, B2 1 -1 -1 1 Y

(6.12) 3 -1 1 1

where Xi is equivalent to the character of the 3 X 3 block matrices of which Using Eq. (6.12), we obtain the following characters for the reducible
the full matrix for the operation is composed. For the operations of C2v the representation I'3,,:
contributions per nonshifted atom for each operation, obtained from the
characters of the individual-atorn block matrices for each operation, are C2v E C2 u(xz) u(yz)

XE = 3, Xc2= -l, Xa\xz) = 1, XO'(yz) = l Ni 3 l 1 3

Xi 3 -1 1 l
Note that the contribution per nonshifted atom for both reflections is the same,
even though the individuai 3 X 3 matrices are different. This is an exampie of a r., 9 -1 1 3
generai result: The contribution per nonshifted atom [or a particular operation is
the same regardless of the orientation o] its associated symmetry elemento From the character for E we see that the dimension of the representation is
Moreover, the value of the contribution per nonshifted atom for a particular op- consistent with 3n = 9. Note that the individuai values of XR of which our f3n
eration is the same in any point group in which that kind of operation is found. is composed are the same as those from the traces of the full 9 X 9 operation
The values of Xi are important enough for this application that they have matrices in Eqs. (6.11)-(6.14).
been tabulated in some texts* Actually, such tables are not needed, since the We will use the tabular method to reduce f3n (cf. Section 3.1). The fol-
values can be obtained easiIy from any character tabIe, such as the one being lowing work sheet incorporates the information needed to generate the re-
used for the molecule under consideration. From an examination of the indi- ducible representation, and it also notes the transformation properties of the
vidual-atorn transformation matrices in Eq. (6.8) through (6.11) we can see unit vectors and rotational vectors from the character table (cf. Appendix A).
that the individuaI elements C'Il, C22, C33 (along the trace of the 3 X 3 matrix)
C2v E C2 u(xz) u(yz)
indicate the effects of the operation on the coordinates x, y, z , respectively, of
the atom on which they operate. Therefore, just Iike the generaI vector v we Ni 3 1 ) 3
considered in Section 2.3, the values for these elements will be identical to Xi 3 -) 1 1
the characters for the operation in the irreducibie representations by which
r., 9 -1 1 3 L n,
the uni t vectors x, y, and z transform. To find a needed value of Xi> then, sim-
ply add up the characters in the character table under the operation for the AI 9 -1 1 3 12 3
irreducible representations by which alI three unit vectors transform. If two A2 9 -1 -1 -- - -3 4 1 R,
z

or three unit vectors transform nondegenerately by the same species (e.g., x B1 9 1 1 -3 8 2 x, R,

and y in C2/1> and x, y, Z in Ci), double or triple the character for that species, B2 9 1 -1 3 12 3 y, Rx
as the case may be, as the contributions of the associated vectors for each op-
eration. If two or three uni t vectors transform degenerately by the same This shows that f3n = 3A1 + A2 + 2B1 + 3B2. Consistent with Eq. (2.10), we
have found nine nondegenerate species for the nine degrees of freedom pos-
*For example, see E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations: The
sible for S02'
Theory o] Infrared and Raman Vibrational Spectra. McGraw-Hili. New York, 1955, Table 6-1, OUI interest is in sulfur dioxide's 3n - 6 = 3 normal modes of vibration.
p. 105. We can find the symmetry species of the genuine norma! modes of vibration
176 Chapter 6 Vibrational Spectroscopy 6.1 Vibrational Modes and Their Symmetries 177

by identifying and removing from r the species for the three translations
311

and three rotations the molecule possesses; that is,

(6.13)

The species comprising ftrans and Cot are the sarne as those of the three unit-
vl(AI)
vector and three rotational-vector transformations, respectively. From the C2v Symmetric stretch
character table, as noted in the worksheet above, we deduce that the transla-
tions are rtrans = AI + BI + B2, corresponding to T" Tç, and Ty, respectively.
Likewise, the rotations are frot = A2 + BI + B2, corresponding to R" Ry, and
R.n respectively. Applying Eq. (6.13) we have fJn-6 = 2AI + B2.
This result tells us the symmetry of the motions that constitute the three
normal modes of S02. Two of the modes preserve the symmetry relationships
implied by the A I representation, which is the totally symmetric representa-
tion of the group. This means that the motions of the atoms in these two nor-
ma! modes maintain the complete set of symmetry relationships of the group
C2v through ali phases of the vibrationa! cycle. The third mode belongs to the
species B2. From the characters of B2 (or from the symmetry and antisym-
metry implied by the Mulliken symbol) we know that this mode is antisym- V3(B2) Figure 6.9 Normal modes of S02. Arrow lengths
Antisymmetric stretch have been exaggerated for clarity.
metric with respect to both C2 rotation and u(xz) reflection.
With only three atoms in the molecule, it is not difficult to deduce the
motions of these three normal modes. For the Al modes, both oxygen atoms table), and among modes of the same symmetry species in descending order
must be moving in phase in the yz plane.* If they were to move out-of-phase, of vibrationaJ frequency* In the case of S02, for example, the two totally
C2 and u(xz) would not be maintained. lf they were to move out of the yz symmetric A I modes are assigned as VIand V2. Stretching modes tend to have
piane, they would cause molecular rotation (Ry if in the same direction, R, if higher frequencies than bending modes, as observed in the case of S02, so
in opposi te directions). With these restrictions, we conclude that there are the symmetric stretch is assigned as VI and the bending mode is assigned as
only two types of totally symmetric motions. The two Al modes must be (a) V2· The B2 antisymmetric stretch, being lower in symmetry, is assigned as V3,
an in-phase stretching and contracting motion primarily along the bond axes despite its having a higher frequency than either VI or V2. The relative order-
(symmetrie stretching mode) and (b) a baek-and-forth bending motion of the ing of observed frequencies tends to be the sa me for various molecules with
O-S-O bond angle (bending mode). Likewise, the B2 mode must be confined the same structure, so the assignment of modes to frequency numbers often
to motions in the yz piane, but the oxygen atoms must be moving in opposi te carries over from one compound to another. For example, H20 is a bent tri-
phases so as to be antisymmetric with respect to C2 and u(xz). The motion atomi c molecule, like S02, so its three normal modes are numerically as-
implied by these restrictions involves contraction of one S-O bond while the signed in the same way [vI(AI) = 3657 cm-I, v2(AI) = 1595 cm"", v3(B2) =
other S-O bond is stretching, and vice versa. This is an antisymmetric streteh- 3756 cm-1].t
ing mode." The forms of ali three normal modes are depicted in Fig. 6.9.
In addition to Mulliken symbol designations, normal modes are usually *For historical reasons, many of which are no longer evident, the numbering for certain well-
identified by frequency numbers as Vh V2, V3, ... (cf. Fig. 6.9). For S02 the ob- known structure types does not follow this convention. For exarnple, the frequencies of octahe-
served frequencies are Vj = 1151 cm-l, l"2 = 519 cm-I, and V3 = 1361 cm-l. dral XY6 are traditionally numbered "I (Alg); ~ (Eg), "3 (h,), "4 (h,), "5 (T2g) , "6 (h,), in
keeping with the older form of the 0" character table (e.g., see G. Herzberg, M olecular Spectra
The numbering is often assigned systematically in descending order of sym-
and Molecular Structure. II. Infrared and Raman Spectra 01 Polyatornic Molecules, Van Nostrand,
metry species (as Jisted down the left column of the appropriate character Princeton, NJ, ·1945, p. 123). Today's character tables Iist gerade species first, then ungerade
species. If the numbering had been based on this ordering, the T2g frequency would be "3. The
*The sulfur atom must also move in opposition to the oxygen atoms to maintain the position of reasoning behind the frequency numbering of some other structures (e.g., XY4 square planar,
the center of gravity of the molecule. Otherwise, translation would result. Nonetheless, for the ZXY 2 planar, ethane-type X2 Y 6, and nonlinear X2 Y 2) is not as apparent. Except for these cases,
present purposes, it is easier to envision the normal modes primarily in terms of the oxygen mo- we will use systematic numbering by symmetry species.
tions, tThe frequencies quoted for botn S02 and H20 are for sarnples in the gas phase, The actual
+Often such modes are called asymmetric, which literally means lacking symmetry. This, of spectroscopic bands show rotational fine structure (P, Q, R branches), subject to quantum me-
course, is not the case. Current practice favors the term antisymmetric, to indicate that the sym- chanical restrictions. In the case of the A I modes infrared bands for the pure vibrations (Q
metry of the motion is in some respects contrary to the complete symmctry of the molecule. branches) are forbidden.
 178 Chapter 6 Vibrational Spectroscopy 6.1 Vibrational Modes and Their Symmetries 179

For simpJe molecules such as 502 and H20 there is a one-to-one corre-
spondence between the number of fundamental frequencies and the number _------i-- , t
t
t
t

of normal modes, because the low molecular symmetry does not allo w de- , , "
,

t t
t

v-,
\ ••• /
..""
f
I
t

generacy. If the molecule belongs to a point group that has doubly or triply r: -/x
t
\ ....
:'.,,---,., ~~_·_,'x
degenerate irreducibJe representations, some vibrational modes may be de- t
\. zv'/~
\ V'\. I I
/

........
r'" "
t

generate and therefore have identical frequencies. In these cases the number .•. ~....
- -, t
I

.•.....
,1 ......•
, I

of frequencies (Vj, ~, V3, ... ) will be less than the 3n - 6 (or 3n - 5, if linear)
normal modes.
As an example of a moJecule with degenerate normal modes, let us con- E
" sider the symmetry of the normal modes of a tetrahedral XY4 molecule (e.g.,
CH4, CCI4, SO~-). Using the approach we detaiJed for 502, we wilI count the
number of atoms that are nonshifted by each operation of the group (Td) and
multiply by the contribution per nonshifted atom for the operation. In the
case of Td the unit vectors x, y, and z transform degenerately as T2, so the -,
\....
-:» I
1"/
'il"
I
I
"
, ••• • / I

contributions per nonshifted atom for the operations are identical to their ';''''" _. .!..~-. -,'x
characters for the T2 representation (cf. character table for Td in Appendix \ \ z'" .•••••.
/~ ~ I
"
A). There is a single character for al! operations of a class, and likewise a sin- r,
- -,
J
, , t

gle vaJue for the contribution per nonshifted atom for all mernbers of the
class. Since there are five classes in Td, we only need to consider five repre-
sentative operations, one from each class, to generate the reducibie repre-
sentation.
Proceeding in this manner, we note that E leaves all five atoms non-
shifted, C3 (and likewise cj) leaves the X and Y atoms on the chosen axis
nonshifted, C2 and S4 (and Iikewise S~) !eave only the centra! X atom non- - -it /7 I
"
shifted, and any Ud leaves the X and two Y atoms in the pIane nonshifted. ,
•
./ '
'
tt
t

L·_·_,X
From this we obtain the following work sheet. t
t
t
Td E 8C3 3C2 6S4 6Ud t
t

Ni 5 2 1 1 3
Xi 3 O -1 -1 1
T2
r., 15 O -1 -1 3 ~ ni Figure 6.10 Normal modes of vibration of a tetrahedral XY4 molecule. [Adapted
with permission from G. Herzberg, Molecular Spectra and Molecular Structure: l!.
A1 15 O -3 -6 18 24 1 lnfrared and Raman Spectra 01 Polyatomic Molecules, reprint 1991 with corrections,
A2 15 O -3 6 -18 O O Krieger Publishers, Malabar, FL.]
E 30 O -6 O O 24 1
T1 45 O 3 -6 -18 24 1 (Rx, n; Rz) The individua! modes giving rise to these four fundamenta! frequencies
T2 45 O 3 6 18 72 3 (x , y, z ) of XY4 are shown in Fig. 6.10* The-ffequency VI is a symmetric stretching
motion, also described as a "breathing" mode. The doubly degenerate V2 fre-
This shows that f3n = Al + E + TI + 3T2. From the listed vector transfor- quency arises from two bending deformations, sometimes described as "skat-
mation properties, f,rans = T2, and fra, = T1. Subtracting the translations and ing on the sphere" of the four Y atoms. The frequency v3 arises from three
rotations we obtain f3n-6 = Al + E + 2T2. Thus, we predict that there should degenerate antisymmetric stretching motions. The frequency V4 arises from
be four frequencies: vj(Aj), ~(E), v3(T2), v4(T2). three bending motions in which opposi te pairs of Y atoms move in opposi te
How can there be only four frequencies if by 3n - 6 we expect nine nor- phases. The composite motion of these three modes is a kind of "urnbrella"
ma! modes? One pair of modes, v2(E), is doubIy degenerate and gives rise to deformation (cf. Appendix C).
a single frequency. Three other modes are triply degenerate and give rise to • Appendix C also shows the forrns of the normal vibrational mcdcs for tetrahedral XY 4, as well as
their own single frequency, v3(T2), whiJe another three modes are triply dee those for some other common structures. In these figure" doubly and triply degenerate modes are
generate arnong themselves and give rise to a different single frequency, v4(T2). shown with a single drawing representing the linear cornbination of the individuai degenerate modes.
180 Chapter 6 Vibrational Spectroscopy 6.2 Symmetry-Based Selection Rules and Their Generai Consequences 181

6.2 Symmetry-Based Selection Rules and We can analyze whether or not an integrai of the form of Eqs. (6.14)
Their Generai Consequences and (6.15) will be nonvanishing 011 the basis of the symmetries of the wave
functions and the components of JL. To do thi we use a generai result of
We have seen in Section 6.1 that the various normal modes of a molecule can quantum mechanics, presented here without proof, that an integra l of the
be catalogued and analyzed in terms of their symmetry with respect to the product of two [unctions, Jfl1f8 d'T, can be nonzero only if it is invariant un-
overall molecular symmetry. The qucstion now arises whether or not these vi- der al! operations of the molecule's point groL/p. This can occur only if the
brations can be obsei ved in the infrared and Raman spectra. What we seek direct produce of f AiB is or contains the totally symrnetric representation of
is a determination of the spectroscopic activity of the normal modes, also the point group. Applying this to the present case, if the integrai for the
called a determination of the spectroscopic selection rules. These se!ection transition moment transforms as the totally symmetric representation, the
rules indicate which norma! modes are active (allowed) or inactive (forbid- vibrational transition will be infrared allowed. Now, the ground-state vibra-
clen) in each kind of spectrum. tional wave function !J;o is totally symmetric for all molecules (except free
The spectroscopic activity of any norma! mode depends upon quantum radicals) and the excited state wave function !J;1 has the symmetry of the
mechanical restrictions that can be analyzed in terms of the symmetry of the norrnal mode. As we have seen in Section 3.5, the direct product of the to-
wave functions involved. For the moment we will confine our discussion to tally symmetric representation with any non-totally symmetric representa-
fundamenta!s, which for any norma! mode involve a transition for which Ilv = tron IS the non-totally symmetric representation (e.g., in C2v, A, X B, =
:t: 1. The basic quantum mechanical selection rule for any such transition is B1)· In the present case this means that by itself the product !J;O!J;1 has the
that lite vibrational transition will have nonrero intensity in either the infrared symmetry of !J;1' However, the product of an irreducible representation with
or Raman spectrum if the appropriate transition moment is nonrero. Norma! itself is or contains the totally symmetric representation (cf. Section 3.5).
modes that do not meet this criterion for one or the other kind of spectrum T?us, if any componen t of JL has the same symrnetry as !J;" the product JL!J;1
cannot be observed directly by that technique. will be totally symmetric and the integrai will be nonvanishing. Since a di-
For inlrared absorption to occur, the normal mode must have an oscil- pole comp~nent can be represented by a vector, we can see that the syrn-
lating molecular dipole moment with the same frequency as the oscillating metry species of JL.n JLy, and JLz are the same as the unit vector transforrna-
clectric ficld of the radiation. In terms of quanturn mechanics, the transition tions x, y, and Z, as listed in the character table. Therefore, a normal mode
mornent for the fundamental of a normal mode (v = O~ v = 1) can be written belonging lo the same symmetry species as any of the unit vector transfor-
mations x, y, or z will be active in the infrared spectrum. In other words, once
M(O, 1) = J !J;oJL!J;, d'T (6.14) we know the symmetries of the normal modes, ali we need to do is look at
where !J;o and !J;l are wave functions for the ground and excited vibrational the unit vector symmetries in the character table to see which modes are in-
states, and JL is the oscillating electric dipole moment vector as a function of frared active.
the normal coordinate for the norma l mode. The normal coordinate, usually In the Raman experiment (Fig. 6.11), incident laser radiation with an os-
given the symbol Q, is a single reference coordinate by which the progress of a cillating electric fie!d E impinges on a sample and induces an electric moment
normal mode can be followed." Absorption will occur if M =1= Q. The vector JL is p in the sample. The induced moment arises because the molecule's electrons
a resultant of its components JL.n JLy' and JLz' so we may rewrite Eq. (6.14) as are attracted toward the positive pole of the field and the nuclei are attracted

Mx = J !J;oJLx!J;, d'T

My = J !J;oJLy!J;, d'T (6.15)

I----+-----?- Scattered radiation

Mz = J !J;oJLl.!J;, d'T
If any one of these components is nonzero, the entire transition moment will
be nonzero.

=For a heteronuclear diatornic molecule, AB, the normal coordinate is expressed in terrns of the
displacernents of the two atoms as Q = Sr A + D.r[J, where D.rll/D.rn = m8/mA. the ratio of the
masses of the atorns. The norma I coordinate expressions are more complex for polyatomic rnol-
ecules. See E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Ma/ecu/al' Vibrations: The Theory o] Incident radiation
Infrared and Raman Vibrational Spectra, McGraw-Hill, New York, 1955, for details. Figure 6.n Typical experimental arrangement for Raman spectroscopy.
182 Chapter 6 Vibrational Spectroscopy
6.2 Symmetry-Based Selection Rules and Their Generai Consequences 183

Both Al and Bz, the species of the three norma! modes, have listings for uni!
to the negative pole. The induced moment is related to the field strength of
vectors and direct products. Therefore, ali three modes are active in both the
the incident radiation by
infrared and Raman spectra. In other words, we should be able to observe
P= aE (6.16) the same three frequencies in both the infrared and Raman spectra.
Likewise, wefound in Section 6.1 that a tetrahedral XY4 molecule has
where the proportionality constant a is the polarizability, whose magnitude
four frequencies for its nine normal modes: vt(A1), vz(E), v3(Tz), v4(Tz)·
changes as the molecu!e oscillates. For a norma! mode to be Raman active
Looking at the character table for T" we find the following unit vector and
there must be a nonzero change in the polarizability with the normal coordi-
direct product transformation properties:
nate at the equilibrium configuration; that is, (aalaQ)o =I=-O. The polarizabil-
ity is best expressed as a tensor, and in this Iorrn Eq. (6.16) can be recast as Td
Al x2 + l + Z2
Az
(6.17) E (2Z2 - X2 - l, xZ - /)

TI
T2 (x, y, z) (xy, Xl, yz)

where aij = aji' If the change in any one of these components is nonzero
Ali three unit vectors transform degenerately as T2, so only norma! modes with
[(aaufaQ)o =I=-O], then the mode will be Rarnan active.
T2 symmetry can be infrared active. For tetrahedral XY 4, this means that only
In terms of the polarizability tensor, the transition moment for Raman ac-
V3 and V4 can be observed by infrared spectroscopy, In contrast, Al, E, and T2
tivity of a fundamental may be expressed as
ali have direct product listings, which means that modes with these symmetries
P(O, 1) = J !J;oaE!J;1 dr = E J !J;Oa!J;1 d-t (6.18) will be Raman active. Thus, we should be able to observe ali four frequencies
by Raman spectroscopy. In summary, we have the following activities:
An integraI of this form can be written for every component aij, giving com-
ponents Pij' If there is any component for which Pij =I=-0, then the entire mo- E
ment will be nonvanishing [P(O, 1) =I=-O], and the transition wilI be Raman ac-
V2
tive. As with the transition moment expression for infrared activity [Eq.
(6.14) and (6.15)], the integrai will be nonzero if it is totally symmetric. As Raman Raman Infrared and Raman
before, !J;o is totally symmetric and !J;I has the symmetry of the normal mode.
Thus, the integraI will be nonzero if !J;I and any component aij have the sarne Note that only the V3 and V4 modes are active in both the infrared and Raman
symmetry. The symmetries of the ai} components are the same as the binary spectra. As such, each is said to be coincident in both spectra. This means that
direct products of vectors, whose transformation properties are listed in the we should expect to find a band for V3 at the same frequency in both the in-
last column of the character table. From this it follows that a normal mode frared and Raman spectra. The same is true for V4. *
will be Raman active if il belongs to the same symmetry species as one of the Given the symmetry-based selection rules, examination of the character
binary direct products of vectors listed in the character table [or the molecule. tables allows us to draw the following general conclusions:
In Section 6.1 we saw that SOz has three norma! modes: vt(At), ~(Al),
v3(Bz). Looking at the character table for C2v, we find the following unit vec- 1. Infrared-active modes can be distributed among no more than three sym-
tor and direct product transformation properties*: metry species, since activity is associated with the transformation proper-
ties of the three unit vectors ..Rarnan-active modes can be distributed
c 2" among as many as [our symmetry species, depending on the point group,
because the direct products typically span two to four species.
AI Z x2 ,l, Z2

A2 xy
BI X XZ * Although coincident bands have the sa me frequency in both infrared and Raman spectra, they
generally do not have comparable intensities. This is a result of the very different phenomena
B2 Y yz
giving rise to the two kinds of spectra: photon absorption for infrared spectroscopy and inelastic
photon scattering for Raman speclroscopy. Thus, for example, a band for a given coincident
mode might be very slrong in the infrared spectrum bUI very weak in the Raman spectrum, or
*The transformations of the rotational vectors R" Ry, and R, have been ornitted, because they
vice versa.
have no relevance to determining infrared and Raman activity.
184 Chapter 6 Vibrational Spectroscopy 6.3 Spectroscopic Activities and Structures of Nonlinear Molecules 185

2. In centrosymmetric point groups (those that have inversion, i), unit vec-
111 i,
tors transform as ungerade species, and direct products transform as ger-
ade species. Therefore, infrared-active modes will be Raman inactive, and
vice versa, for centrosymrnetric molecules. In other words, the infrared
and Raman spectra of centrosymmetric molecules should have no funda-
mental frequencies in common. This requirement is known as the rule of
mutual exclusion.
3. Unit vector and direct product transformations do not span all species in
some groups. Thus, some irreducible representations are not associated t
with either a uni t vector or direct product transformation. Nonetheless,
the molecule may have a normal mode that transforms by one of these
species. Thus, ù is possible to have some normal modes that cannot be ob-
served as fundamentals in either the infrared or Raman spectra. These
spectroscopically inactive modes are often called silent modes.
4. The totally symmetric representation in every point group is associated
with one or more direct product tr ansformaticns. Therefore, normal Figure 6.12 Raman band intensities
modes that are totally symmetric will always be Raman active. Totally syrn- 111and Il. of CC14 far 111 (top) at 458
cm-I and 112(bottom) at 218 cm-I.
metric modes may or may not be infrared active, depending on the point
The 111 band shows isotopie splitting
group. ~ Frequency due to 35Cl and 37CI.
Normal modes that are totally symmetric can be identified experirnen-
tally in the Raman spectrum by measuring the depolariration ratio, p. As band for which p = 3/4 is said to be depolarized. In practice, for highly syrn-
shown in Fig. 6.11, the scattered Raman radiation has a polarization that can metric molecules one often finds p = O for polarized bands. This makes it very
be resolved into two intensity components, 1.1 and lU, whose polarities are re- easy to assign such bands to totally symmetric modes, even without calculat-
spectively perpendicular and parallel to that of the exciting laser radiation. ing the ratio. On the other hand, owing to experimental imperfections, one
The intensities of the separate components far each spectroscopic band can often finds that p is only approximately 3/4 far depolarized bands from non-
be observed by using a Polaroid analyzer (e.g., a piane polarizing camera lens symmetric modes. Nonetheless, these deviations rarely cause confusion when
filter). The spectrum is recorded with the analyzer in one orientation, say 1U, making assignments. Figure 6.12 shows the intensities in both the In and I l.
and then recorded again in the other orientation, 1.1' Using the recorded band orientations for the 1I1(Al) and Vz(E) Raman bands of CCI4· As can be seen,
intensities, the depolarization ratio can be calculated as in the 1.1 orientation the 1I1(A1) band virtually vanishes. Carefully obtained
values show that p = 0.005 ± 0.002 far 111 (A I) and p = 0.75 ± 0.02 for Vz(E).
p = ls. (6.19)
1U
The value of p depends upon the symmetry of the polarizability, a, as it os- 6.3 Spectroscopic Activities and
cillates with the particular normal mode. In liquid and gas samples, with Structures 01 Nonlinear Molecules
which we are concerned here, the polarizability tensor far an individuaI mol-
ecule is randomly oriented. Therefore, throughout the sample ali possible ori- We have seen in the preceding sectiorrs Ihat the number and spectroscopic ac-
entations are represented. In terms of Eq. (6.16), when the oscillating electric tivity of normal modes depends upon the molecule's symmetry. On this basis
vector of the incident radiation, E, interacts with the sample, the resulting in- we might expect that infrared and Raman spectroscopy couldbe used to dis-
duced moment, P, is the result far the average of ali orientations of a. For tinguish between two or more possible structures that a particular molecule
plane-polarized incident radiation, as produced by lasers, it can be shown might have. Indeed, this approach has been taken for many simple molecules.
from scattering theory that the measured depolarization ratio from such sarn- Of course, as molecular complexity increases and symmetry decreases the abil-
ples should have (a) a value in the range O < P < 3/4 for any mode that is to- ity to distinguish between various proposed structures diminishes, since the
tally symmetric and (b) the fixed value p = 3/4 for any mode that is not to- predicted nurnbers and activities of normal modes are likely to be nearly the
tally symmetric. A band for which O < P < 3/4 is said lo be polarit.ed, and a same. Moreover, the ability to observe any predicted distinctions experimen-
 6.3 Spectroscopic Activities and Structures 01"Nonlinear Molecules 187
186 Chapter 6 Vibrational Spectroscopy

tally also declines. onetheless, within the limitations of relatively small mol- leaves r3n-6 = A Ig + BIg + B2g + A2" + B2" + 2E", for a total of seven ex-
ecules in gas and liquid samples, predictions from symmetry and group theory pected frequencies. From the unit vector and direct product transformations
can be effective tools to interpret vibrational spectra and deduce structures. Iisted above we obtain the following activities:
Suppose we consider a compound whose molecular formula is XY4' As Alg Big BZg B2" 2E"
A2"
we have seen, if the molecule is tetrahedral we should expect the 3n - 6 :=: 9
normal modes to give rise to four fundamental frequencies, ali of which are VI V2 114 Il} 115 V6,1I7

active in the Raman spectrurn, and two of which are also active in the infrared Raman Raman Raman I nfrarecl Infrarecl
spectrum. Furthermore, the Raman band for VI (A l) should be polarized. We (poI)
can summarize these predictions as follows:
The forms of these normal modes are shown in Appendix C. Note that only
VI (Alg), the symmetric stretching mode, preserves the complete symmetry of
Infrared 2 (2T2) D4h. Therefore it is the only mode expected to have a polarized band in the
Raman 4 (AI, E, 2T2) Raman spectrum (indicated "poi" in the table above). The two doubly de-
Polarized l (AI) generate frequencies, V6 and V7, each consist of a pair of normal modes whose
Coincidences 2 (2T2) individuai motions are at right angles to one another in the piane of the mol-
ecule. The motions depicted for V6 and 117 in Appendix Care linear cornbi-
This, then, sets the pattern of spectroscopic activities that characterizes a nations of the pairs of modes in each case. Notice that one of the norma l
tetrahedral XY4 molecule. modes, vs(B2u), which might be described as a deformation of the molecular
Now suppose we consider the possibility that XY4 might be square pla- piane, is not active in either spectrum; that is, it is a silent mode. Therefore,
nar; that is, instead of seven frequencies, we should expect to observe only six directly:
Y three in the Raman spectrum and three in the infrared spectrum.
I These predictions contrast significantly with those for a tetraheçlral
Y-X-Y structure:
I
Y

Counting nonshifted atoms from each operation and using the contributions Infrared 2 (2T2) 3 (A2 2E,,)
11>

per nonshifted atom in each case (the sum of Az,. and E characters), we ob- Raman 4 (AI, E, 2T2) 3 (A I"" Big, B2g)
tain the following work sheet: Polarized l (AI) 1 (A Ig)
Coincidences 2 (2T2) None
ti; E 2C4 C2 2C2 2C;; i 254 a; 20"v 20"e/ Silent modes None 1 (B2,,)

Ni 5 1 1 3 1 1 1 5 3 1
-1 1 1 First, there are three more frequencies than for a tetrahedral species. Second,
Xi 3 l -1 -1 -1 -3 1
l n, as a centrosymmetric molecule, planar XY 4 is subject to the rule of mutuai
r., 15 1 -1 -3 -1 -3 -1 5 3 1
excJusion; that is, none of the Raman frequencies is active in the infrared
-1 -6 -2 -3 -2 5 6 2 16 1 X2 + y2,; spectrum and vice versa. These predictions suggest that it shouId be possible
Alg 15 2
A2g 15 2 -1 6 2 -3 -2 5 -6 -2 16 1 R, to distinguish between tetrahedral andsquare planar XY4 structures on the
16 X2 _ y2
BIg 15 -2 -1 -6 2 -3 2 5 6 -2 l basis of the infrared and Raman spectra. Although the numbers of bands and
15 -2 -1 6 -2 -3 2 5 -6 2 16 1 xy
B2g polarized Raman bands are not greatly different between the two models, the
Eg 30 O 2 O O -6 O -lO O O 16 1 (Rx, Ry) (xz , yz)
predicted absence of coincidences for the square planar structure probably
15 2 1 -6 -2 3 2 -5 -6 -2 O O
Al" would be a most telling distinction. Indeed, considerations of this sort were
15 2 1 6 2 3 2 -5 6 2 32 2 z
A2"
-2 -5 -6 2 O O used as part of the early verification of the tetrahedral structure of CH4. *
BI" 15 -2 1 -6 2 3
-2 1 6 -2 3 -2 -5 6 -2 16 1 If one or more atoms in a compound are substituted by some other ele-
B~" 15
30 O 2 O O 6 O lO O O 48 3 (x, y) ment, the symmetry often changes and with it the vibrational selection rules.
E"
From this we have r3n = A1g + A2g + BIg + B2g + Eg + 2A2u + B2 /l + 3Et<" "See G. Herzberg, Molecular Spectra and Molecular Structure. I/. lnfrared arul Raman Spectra
of Polyatomic Molecules, Vari Noslrand. Princeton, NJ, 1945, pp. 306-307.
Subtracting the species of the rotations and translations, as indicated above,
 188 Chapter 6 Vibrational Spectroscopy 6.3 Spectroscopic Activities and Structures of Nonlinear Molecules 189

For example, consider substituting one hydrogen atom in CH4 with a deu-
terium atom to produce CH3D. While the new species is essentially tetrahe-
dral, the fact that the deuterium atom is approximateIy twice the mass of the
VI' V2, V3' V4 R(pol), i.r.
hydrogen atom reduces the symmetry to Ck ConsequentIy, the number of vi-
(vj, Vza, V3a' v4al
brational frequencies and their activities are those appropriate for this new R(pol) VI
point group. We couId determine the new selection rules de novo, but CH4
and CH3D are closeIy reiated by their group-subgroup relationship Tel --7 C3v'
Thus, we can think of the frequencies of CH3D as arising from perturbations R
of the CH4 frequencies, caused by the descent in symmetry. This suggests a R, i.r.
correiation approach, making use of the correlation table in Appendix B that
Iinks the symmetry species of T" and C]v- R, i.r.
R, i.r.
Taking this approach, we can construct the correlation diagram shown in VB' Vy

Fig. 6.13_ The nondegeneracy of the A1 mode ())1) and the double degener- (V3c' v4J
acy of the E modes ())2) are retained with the descent in symmetry, but the Figure 6.14 Correlation diagram for the normal modes of CH4 and CH2D2· CH2D2
threefold degeneracy of the T2 modes ())3 and ))4) is lifted to become a non- frequencies are indicated by their appropria te numbers for C2v and the correspond-
degenerate A I mode and a pair of doubly degenerate E modes in the new ing numbers for CH4 (in parentheses).
point group C3v' In both cases, deuterium substitution causes one of the three
degenerate modes to acquire a unique frequency from the remaining two. We can summarize these results for CH4~ CH3D, and CH2D2 as follows:
Thus the four frequencies of CH4 become six frequencies for CH3D. The nor- CH3D CH2D2
CH4
mal modes of these six frequencies (cf. XY3Z in Appendix C) have AI and E Td C3v C2v
symmetries, both of which in C3v are associated with unit vector and direct
product transformations (cf. character table in Appendix A). Thus, al! six Ire- Infrared 2 (2T2) 6 (3Aj, 3E) 8 (4AI, 2BI, 2B2)
qucncies of CH3D are active in both infrared and Raman spectra. Of these, Raman 4 (Ai> E, 2T2) 6 (3AJ, 3E) 9 (4A 1, A2, 2B[, 2B2)
the three with A I symmetry should be polarized in the Raman spectrum. Polarized l (AI) 3 (3A
j) 4 (4A1)
We can take the same approach with CH2Dz, using the correlation from Coincidences 2 (2T2) 6 (3Aj, 3E) 8 (4AI, 2BI> 2B2)
T" to CZv (Appendix B). The CZv group does not allow degeneracy, so al! de-
generate modes are spIit into distinct modes with unique frequencies on de- These predictions agree well with the observed frequencies for CH4, CH3D,
seent from T" (Fig. 6.14). Thus ali nine normal modes of CHzDz ha ve corre- and CH2D2 (Table 6.1).
sponding individuaI frequencies. From the transformation properties listed in Note that we could not use our results for CH3D to cane late directly to
the CZv character table, we conclude that eight are both infrared and Raman CH2D2. Instead we began again with CH4_ This was necessary because there
active, but the Az mode is exclusiveIy Raman active. is no group-subgroup relationship between C3v and C2v- By the same restric-
tion, we could not deduce the number of frequencies and activities for square

CH4 CHp Table 6.1 Relationships Among Vibrational Frequencies (cm-I) of CH4, CH3D, and CH2D2.a
(T(/) (C3J
CH4 (Td) lJl(A1) lJ2(E) lJ3(T2) lJ4(T2)
R(pol) VI AI AI VI' v2, v3 R(pol), i.r. .-- .-
(vI' v3a' v4a)
2914 1526 3020 1306
CH3D (C3v) lJ2(A1) lJs(E) lJl(A1) v4(E) lJ3(AI) lJ6(E)
R v2 E E v4, vs, v6 R, i.r. 2205 1477 2982 3030 1306 1156
(v2, v3hc' v4òC>
CH2D2 (C2v) lJ2(AI) lJ3(A1) lJs(A2) vl(AI) lJ6(B1) lJ8(B2) lJ4(A1) lJ?(BI) lJ9(B2)
R, i.r. v3, v4 T2 2139 1450 . 1286 2974 3030 2255 1034 1090 1235
I
Figure 6.13 Correlation diagram for the normal modes of CH4 and CH3D. CH3D
frequencies are indicated by their appropriate nurnbers for C'v and the correspond- "Data tram K. Nakamoto, Infrared Spectra o] Inorganic and Coordination Compounds, 2nd ed.,
John Wiley & Sons, New York, 1970, p.Il3.
ing nurnbers for CH4 (in parentheses).
190 Chapter 6 Vibrational Spectroscopy 6.4 Linear Molecules 191

planar XY4 by correlation with the tetrahedral case, because T" and D4h do D~h
not have a group-subgroup relationship. In al! such cases, where a group-sub-
group relationship does not exist, a direct correlation among chemically re- Ag --------- L; V J, V2 R(pol)
lated structures is not possible. However, if two chemical structures share a
common subgroup, a correlation through that subgroup may be possible.

6.4 Linear Molecules

The procedure we have seen for nonlinear molecules can be applied to linear
cases. The reducible representation I'3n is constructed in the same way, but
only five nongenuine modes (three translations and two rotations, R, and Ry)
are subtracted to obtain the representation for the 3n - 5 norma! vibrational
modes, f3n-5. However, to reduce this representation we must circumvent the V6a,V7a B ,, _

problem of the infinite order of the molecule's point group (either D"'h or
2
_________ n'I
C"'v), since Eq. (3.1) is meaningless when h = 00. As discussed in Section 3.4,
it is convenient to set up the problem in a finite subgroup (usually either D2h V6b' V7b B3u
or C2v) and carry out the reduction in that group. After subtracting the trans- Figure 6.15 Correlation from the working group D2h to the true group D"'h for the
lations and rotations, the results in the finite group can be correlated to the normal modes of C302.
actual infinite-order group, using Table 3.8 (Cc"v *"-7 C2v) or Tab!e 3.9
(D 001" *"-7 D2h). The activities of the normal modes can be deterrnined, as be- mations Z2 and (xz, yz), respectively, indicating that the normal modes with
fore, from the unit vector and direct product listings in the character table for these symmetries are Raman active. The two modes with 2:;
symmetry, the to-
D"'h or Coov, as appropriate. tally symmetric representation, will be polarized. Likewise, we see that and 2:~
As an example of this approach, consider C302, carbon suboxide: TI" are associated with the unit vector transformations z and (x, y), respec-
.. .. tively, indicating that the normal modes with these symmetries are infrared ac-
O=C=C=C=O
" .. tive. Note that C302, being a centrosymmetric molecule, is subject to the rule
This is a centrosymmetric linear molecule, so the point group is Dooh' To avoid of mutuai exclusion, so the infrared-active normal modes are not Raman ac-
the problem of the group's infinite order, we will set up the representation I'3n tive, and vice versa. In surnmary, our predictions for C302 are as follows:
in D2h, taking the molecular axis as z. By counting nonshifted atoms and mul-
tiplying by the contributions per nonshifted atom for each operation, we ob-
tain the following results: Infrared 4 (2'2:~ + 2nl<)
Raman 3 (2'2:; + flg)
o-(xy) o-(xz) o-(yz)
Polarized 2 (2'2:; )
Ni 5 Coincidences None
5 l 1 l 1 5 5
Xi 3 -l -l -l -3 1 l l
The infrared and Raman spectra of C302 are consistent with these expecta-
f3n 15 -s -1 -l -3 5 5 tions. However, demonstrating that the spectra were uniquely consistent with
a linear structure proved to be a less-than-straightforward task in this case.
This reduces as I' 3" = 2Ag + 2B2g + 2B3g + 3B lu + 3B2" + 3B3", which has As a result, the linear geometry of C302 was for many years in doubt, since
the required dimension of 15. By inspecting the unit vector and direct product the spectra are complicated and could be plausibly interpreted on the basis
listings in the D2h character table we determine that ftrans = B1u + B2u + B3" of alternative structures. Indeed, the controversy over the structure of C302
and frot = B2g + B3g. Note that fret is composed of only the two species cor- provides a case study of the difficulties that can be encountered in using vi-
responding to R; and Ry, not R, (Big)' Thus, f3n-5 = 2Ag + B2g + B3g + brational spectra for structure elucidation. *
2131" + 2B2" + 2B3", which has the required 3n - 5 = 10 dimension. Using
Table 3.9 we can construct the correlation diagram shown in Fig. 6.15, which *See F A. Miller, D. H. Lemmon, and R. E. Witkowski, Spectrochim. ACla, 1965, 21, 1709; and
shows that in Dooh f3n-5 = 22:; + TIg + 22:~ + 2TIu. From the Dooh character W. H. Smith and G. E. Leroi, 1. Chem. Phys., 1966,45, 1765, as we!! as earlier references cited
table we see that 2:; and TIg are associated with the direct product transfor- in these papers.
192 Chapter 6 Vibrational Spectroscopy 6.5 Overtones, Combinations, and Other Complications 193

6.5 Overtones, Combinations, and Other Complications of the binary direct products listed in the last column of the appropria te char-
acter table. Although these basic selection rules allow spectroscopic activity
We have seen that it is possible to predict the number and spectroscopic ac- for many overtones and combinations, generally only a few have sufficient in-
tivities of the fundamental transition of the norma l modes of a polyatomic tensity to be observed. They tend to be more prevalent in the infrared than
molecule. When applying these predictions to actual spectra a number of the Raman spectrum. In light of this, spectroscopic selection rules are not
complications can arise. On the one hand, weak intensities or instrumental used to predict the numbers of such bands in the spectra, but rather to justify
Iimitations can result in fewer observable frequencies than predicted. But an assignment of a suspect weak bando The question becomes "Is this over-
more often there are more peaks in the spectrum than one would predict for tone or combination allowed in this spectrum?" With these kinds of bands,
the structure. Several factors can give rise to additional peaks in the infrared more than with fundamentals, the selection rules tell what can be, rather than
and Raman spectra, the most common being the presences of overtone bands what probably will be.
and combination bands. The symmetries of overtones and combinations can be determined by
Although the fundamental selection rule for a harmonic oscillator allows taking the direct products of the irreducible representations of the funda-
only transitions for which Llv = ± l, anharrnonicity in the oscillations of real mentals involved. From the properties of direct products discussed in Section
molecules gives rise to weak spectroscopic bands from transitions for which 3.5, we can anticipate that the resulting representation will be irreducible if
Llv = ± 2, ± 3, ... , ± n. For a norma I mode Vi> such transitions represent the one or both of the component fundamentals of the overtone or combination
first, second, and succeeding overtones of the fundamental, customarily des- are nondegenerate. If both components are degenerate, the direct product
ignated 2v;, 3vj, ... , nv.. The probabilities of these transitions, and hence their will be a reducible representation, requiring decomposition into its compo-
band intensities, fall off rapidly with higher LlV, so generally only first and (to nent irreducible representations. We can combine our knowledge of the gen-
a lesser extent) second overtones are encountered in routine work. The ob- erai properties of direct products with the symmetry-based infrared and
served frequencies of overtones are nearly the appropria te whole number Raman selection rules developed in Section 6.2 to make some generai pre-
multiplies of the frequency of the corresponding fundarnental. However, since dictions about the activities of overtones and combinations. As we develop
the spacings between successive levels of an anharmonic oscillator are pro- these generalizations, we will illustrate with specific examples from the in-
gressively smaller (cf. Fig. 6.3), overtone frequencies are almost always slightly Irared and Raman spectra of CH4, taken from data listed in Herzberg's book.*
less than the whole-nurnber multiple values. For reference, the fundamental frequencies of CH4 are listed in Table 6.1.
lt is also possible far excitations of two separate normal mode to cou- Recall that the direct product of any nondegenerate irreducible represen-
pie, giving rise to combination bands of the type Vk + Vj. Less commonly, tation with itself is the totally symmetric representation. From this we may
combinations with and among overtones, having the generaI form nVk + mv., conclude that the first overtone of any nondegenerate normal mode will be-
can be observed. There can also be subtractive combinations, called differ- long to the totally symmetric representation. Since the totally symmetric rep-
ence bands, such as Vk - Vj, or more generally nVk - mv.. As with overtones, resentation is always the symmetry species of at least one component of the
intensities of both summation and difference combinations are typically much polarizability tensor, we may conclude that al! first overtones of nondegenerate
less than those of fundamentals. This is especially true for combinations in- norma! modes will be Raman allowed. Furthermore, inspection of the charac-
volving overtones or differences. In most cases, owing to anharmonicity, the ter tables reveals that first overtones will be infrared [orbidden, excepl for mol-
observed frequencies tend to be slightly lower than the numerical sum or dif- ecules belonging to the point groups CI, Ci, C and C II, OnIy these small
l1v
•

ference of the frequencies of the combined fundamentals. groups have at least one of the unit vectors transforming as the totally syrn-
Spectroscopic selection rules far overtones and combinations follow the metric representation. In the case of CH4, the only nondegenerate fundarnen-
same considerations as those we have applied to fundamentals. For infrared tal is VI = 2914 cm -I. By what we have just seen, we might expect an overtone
activity, an expression for the transition moment M, in the form of Eq. (6.15), 2vI in the Raman spectrum near 2 X 29"14 cm-I = 5828 cm-I. However, none
must be nonzero. For Raman activity, an expression far the transition mo- has been reported, probably owing to extremely weak intensity. This is an il-
ment P, in the form of Eq. (6.18), must be nonzero. Thus, an overtone or lustration of the point previously made that the selection rules for overtones
combination will be infrared allowed if it belongs to the same irreducible rep- and combinations are merely permissive or prohibitive, and not predictive.
resentation as one or more components of the electric dipole, equivalent to The direct product of any degenerate representation with itself contains
the symmetry species of the unit vectors listed in the next-to-last column of the lotally symmetric representation along with other irreducible representa-
the appropriate character table. Likewise, an aver tane or combination will be
Raman allowed if it belongs to the same irreducible representation as one or "G. Herzberg, Molecular Spectra and Molecular Structure. l!. lnfrared and Raman Spectra of
more components of the polarizability tensor, equivalent the symmetry species Polyatomic Molecules. Van Nostrand. Princeton. NJ, 1945. p. 308.
194 Chapter 6 Vibrational Spectroscopy 6.5 Overtones, Combinations, and Other Complications 195

tions. Therefore, we can extend the previous generalization to all fundarnen- 1306 cm-I = 4326 cm-I), and another at approximately 1720cm-1 has been
tals; i.e., al! [irst overtones are Raman allowed. Such overtones may be in- assigned to V4 - lJ3(cf. 3020 cm-I - 1306 cm-1 = 1714 cm-l).
frared allowed as well, without restriction to certain point groups, depending The assignment of overtone and combination bands is usually uncertain,
on the other symmetry species that may compose the reducible representa- particularly when degenerate modes are involved. In such cases, anhar-
tion. For example, consider the possible activities of 21'3 and 2V4 of CH4. Both monicity may cause splitting into sub-bands that correspond to the individuai
fundamentals belong to T2, and as such are active in both infrared and Raman symmetry species comprising the direct product. Even without this complica-
spectra. The direct product of T2 with itself is tion, assignment is often ambiguous and must be regarded as tentative. Often
several allowed overtones and combinations may have potentially similar fre-
E quencies or may be obscured by stronger fundamentals. Of course, none is
3 o -1 -1 1
expected to ha ve much intensity, which makes such bands difficult to discern
3 O -1 -1 1 above the spectroscopic noise.
Even with these complications, overtones may give useful information
9 O 1 1 not readily available by other means. Recall that for a planar XY4 species
there is one norma l mode, lJs(B2,,), which is not active in either infrared or
This reduces as [(T2T2) = Al + E + T1 + T2. As expected, this contains the Raman spectra (cf. Section 6.3). However, the first overtone of this mode
totally symmetric representation, Al, but il also contains E and T2, which are should be totally symmetric (A1g) and allowed in the Raman spectrum. In the
likewise symmetry species of polarizability tensor components. Thus, the case of XeF4, a weak feature at 442 cm -I in the Raman spectrum has been
overtones 2V3 and 2V4 are Raman allowed by virtue of the three components assigned to 2 vs, implying that Vs is approximately 221 cm -1.* This value is
Al + E + T2. The T2 species is the only one in Td that is associated with in- reasonable, given the other observed frequencies. This fortuitous observation
frared activity, so these overtones are also infrared allowed. The symmetry is virtually the only way to estimate the value of vs from the spectra.
species T1>which is also a component of [(T2T2), is not associated with ei- Although generally weak, overtones and combinations can sometimes
ther infrared or Raman activity and can be ignored for the present purposes. have surprisingly strong intensities when they fall near a fundamental with
Herzberg lists 2V3 as 6006 cm-1 (cf. 2 X 3020 cm ? = 6040 cm-l) and 2V4 as the same symmetry. In these cases, the overtone or combination "borrows''
2600 cm-l (cf. 2 X 1306 cm-1 = 2612 cm-l) from infrared data. intensity from the fundamental. The two bands mix and split, losing their in-
The activities of combinations can be determined in similar manner. dividuai identities. One feature moves to higher frequency and the other to
Consider the combination lJ2+ V4 of CH4. The species of the two fundamen- lower, with both having comparable intensities. The phenomenon is known as
tals are E and T2, respectively, and their direct product is Fermi resonance. Fermi resonance is a necessary consequence of symmetry. If
two different states with the same symmetry were to have equal energies, this
E would imply a degeneracy higher than that of the states' symmetry species.
2 -1 2 O O For example, if a totally symmetric fundamental were to have the same fre-
3 O -1 -1 1 quency as a first overtone of a nondegenerate fundamental (also totally sym-
metric) there would exist a double degeneracy for a nondegenerate syrnme-
6 O -2 O O try species (the totally symmetric representation). This is an oxymoron.
Moreover, it is forbidden by the symmetry of the system. Therefore, acciden-
This reduces as [(ET2) = TI + T2. This combination contains T2, so it is both tal degeneracy among states with the same symmetry is [orbidden. By mixing
infrared and Raman allowed. Again, the TI component can be ignored. An and separating the two states, Fermi resonance avoids the symmetry contra-
infrared band at 2823 cm-1 has been assigned to this combination (cf. diction that would otherwise occur. .- -
1526 cm-I + 1306 cm-1 = 2832 cm-l). A well-known case of Fermi resonance occurs in the Raman spectrum of
The activities of difference bands are determined in the same way as the CCl4 (Fig. 6.16). The fundamental v3(T2) has a frequency cf 776 cm -l The
positive combinations. The symmetries of both positive and negative cornbi- combination VI + lJ4has the same symmetry (Al T2 = T2) and on the basis of
nations are the same. Thus, if a combination for Vk + Vi is allowed or forbid- normal coordinate analysis has an expected frequency of 459 + 314 cm -1 =
den, then a combination for Vk - Vi is likewise allowed or forbidden. For ex- 773 cm -t, which is virtually the same as V3, given the breadth of the bands.
arnple, combinations v3::'::: lJ4for CH4 ha ve the symmetry r(T2T2) = Al + As a result, lJ3and lJj + lJ4mix to form a Fermi resonant doublet. The Fermi,
E + TI + T2 and are allowed in both infrared and Raman spectra. An in-
frared band at 4313 cm-1 has been assigned to lJ3 + V4 (cf. 3020 cm-1 + *H. H. C1aassen, C. L. Chernick, and J. G. Malm, I Am. Chern. Soc., 1963,85, 1927.
 ì 6.5 Overtones, Combinations, and Other Complications 197
196 Chapter 6 Vibrational Spectroscopy

abundances. In such cases, some spectroscopic bands may appear as multi-

plets. Although it is customary to refer to this fine structure as splitting, in re-
ality it is merely the superimposition of frequencies from the same or sirnilar
modes of ali the possible isotopically substituted molecular species. The ef-
fect tends to be most noticeable when relatively light atoms are involved,
since the masses among the isotopes are significantly different. We have seen
the effect of deuterium substitution on the vibrational frequencies of CH4
(Section 6.3), where mD/mH = 2. In a naturally occurring sampie of methane
the isotopic abundance of 'n is only 0.015%, so band splitting from the pres-
ence of CH3D, CH2D2, CHD3, and CD4 is undetectable. However, if the com-
pound contains elements such as boron (20% lOB, 80% 11B) or chlorine
(75.77% 35C1, 24.23% 37Cl), some bands may show fine structure from the
600 500 400 o mix of isotopically substituted species in the sample. Bands arising from nor-
800 700
cm-l
mal modes in which the isotopically substituted atoms have highest arnplitude
(e.g., stretching modes) are most likely to show splitting.
Figure 6.16 Medium resolution Raman spectrum of liquid CCl4 showing the Fermi
doublet of )13 and )11 + V4 with maxima at 762 cm -1 and 790 cm -I. Neither band can The band for VI in the Rarnan spectrum of CCl4 at high resolution (Fig.
be assigned exclusively to one component. 6.18) shows components from ali possible isotopically substituted species:
C 3sC14, C 37C1 35C13, C 37C12 35C12, C 37C1] 35Cl, C 37C14. The actual symme-
doublet, shown in Fig. 6.16, has maxima at approximately 762 cm -1 and tries of the various components are Td, C3v, and C2v, depending on whether
790 cm-l. Neither of these bands can be assigned exclusiveIy to lI3 or III + lI4' they have four, three, or two atoms of one of the isotopes. However, the mass
The position of the fundamental lI3 can be estimated from the trough between differences between 35CI and 37C1 are relatively small (m37/m35 = 1.03), so ali
the two bands. The same Fermi doublet is also infrared active by virtue of its molecules are virtually tetrahedral. The observed peaks arise frorn essentially
T2 symmetry and is easily observed (Fig. 6.17). the same symmetric stretching motion frorn each isotopically substituted rnol-
In addition to overtones, combinations, and Fermi resonance, "extra" ecular species. Other bands in the spectrum are too broad to show compara-
peaks may appear in the spectrum from isotopic splitting if one of the ele- ble fine structure.
ments in the compound exists as two or more isotopes with relatively high

100 ~-------

% T 50"'"

900
VJ
o L-_L-,_L-,---.-.J
800 700 600 Figure 6.17 Infrared spectrum of the Fermi doublet
480 460
\ 440 Figure 6.18 High-resolution Raman spectrum of the
symmetric stretching band (VI) of CCI4.
cm-I of CCl4.
 Problerns 199
198 Chapter 6 Vibrational Spectroscopy

[See D. E. Irish, A. R. Davis, and R. A. PIane, 1. Chem. Phys. 1969, 50, 2262;
Problems D. E. Irish and G. E. Walrafen, I. Chem. Phys. 1967, 46, 378; R. E. Hester and
R. A. Piane, I. Chem. Phys. 1964,40, 411.)
6.1 Determine the number of frequencies, their symmetries, and the infrared and
(a) Assign the Iour frequencies of the "free " nitrate ion by frequency number (V1,
Raman activities of the norma I modes for the following molecules. Indicate the
v2, v3, V4) and symmetry species. The numbering in this case is systematic by
number of polarized Raman bands and the number of frequencies that should be symmetry species, giving priority to non degenerate modes.
coincident between the two spectra. Representations of the norma I modes for (b) Whether or not solvent water is involved, anion-cation association reduces
these structures can be found in Appendix C. (a) NH3, (b) FeCI~-, (c) H2CO,
the effective symmetry of NO}, causing certain of the spectroscopic bands to
(d) PF5, (e) C2H6 (staggered configuration), (f) H202· split into two components. Two geometries of cation-anion association are
6.2 Determine the number of frequencies, their symmetries, and the infrared and plausible: (1) association along the C3 axis of the NO} ion and (2) association
Rarnan activities of the norma I modes for the following molecules. Indicate the in the NO} ion piane to one of the oxygen atoms. Predict the changes in the
number of polarized Raman bands and the number of frequencies that should be infrared and Raman spectra that would occur with each of these modes of
coincident between the two spectra. (a) SeF s,(b) AsF4, (c) BeF;-, (d) OSF4, association.
(e) lrans-FNNF, (f) cis-FNNF, (g) S20~- , (h) B2H6· (c) In 7.2 M Ca(N03)2 solution, where direct cation-anion association has been
6.3 H. D. Rix [I. Chem. Phys., 1954,22, 429) interpreted incomplete vibrational data postulated, six Raman frequencies have been observed: 1450 cm -J, 1358 cm-l,
for C302 on the basis of a C2h structure. Determine the number of frequencies, 1052 cm -I, 823 cm -I, 743 cm -I, 717 cm -1 The band at 1052 cm -I. is strongly
symmetries, infrared and Raman activities, and the nurnber of polarized Raman polarized, and the bands at 1358 cm-1 and 743 cm-I appear to be weakly
bands expected for this structure. Compare these results to those predicted for polarized. From these data, which of the two modes of association appears to
linear C302 (cf. Section 6.4). occur in concentrated calcium nitrate solutions? [See D. E. Irish and G. E.
6.4 There are several other structures that one might propose for XY4 rnolecules, be- Walrafen, J. Chem. Phys. 1967,46, 378.)
sides tetrahedral and square planar. Determine the number of frequencies, their (d) The laser Raman spectra of 0.3-2.3 M AI(N03)3 solutions show an overtone
symmetries, the infr ared and Rarnan activities, number of polarized Raman at approximately 1660 cm -) of the infrared-active fundamental at 830 cm-)
bands, and coincidences for the following alternative structures. [Hint: You may ("free" ion). Explain why the overtone can be observed in the Raman
find it more expedient to use a correlation from either tetrahedral XY 4 or square spectrum, but its corresponding fundamental cannot. Why is this overtone not
observed in the infrared spectrum? [See W. L. Grossman and G. Chottard,
planar XY 4, as appropriate.)
Spectrochim. Acta 1970,26, 2379.)
(a) A distorted tetrabedron, as predicted by VSEPR theory for four bond pairs
and one Ione pair about the centrai X atom 6.8 Justify or refute the following generalizations:
(b) A distorted tetrahedron resulting from slightly squashing a perfect tetra- (a) Ali even-number overtones (2v;, 4v;, ) are Raman allowed.
hedron along one of its C2 axes (b) Ali even-number overtones (2 V;, 4v;, ) are infrared forbidden.
(c) A square pyramid in which the X atom is at the apex (c) If a normal mode is infrared active, its odd-nurnber overtones (3v;, 5 V;, ... )
(d) Planar XY4 with two Irans-related bonds longer than the other two will be infrared allowed.
6.5 Using a correlation approach, show the relationships among the normal modes (d) Ali combinations between a totally symmetric fundamental and any other
and their infrared ancl Raman activities for the substituted octahedral structures fundamental (vs ± v;) will be allowed or forbidden in the same manner as the
I, II, IlI, and IV in Fig. 3.1. Summarize your results in a table listing infrared ac- nonsymmetric fundamental (Vi).
tive frequencies, Raman active frequencies, polarized Raman bands, and coinci- (e) Ali combinations between a totally symmetric fundarnental and the first
overtone of any other fundamental (vs ± 2v;) wiU be Rarnan allowed.
dences.
6.6 Determine the number of frequencies, their symmetries, and the infrared and 6.9 The following frequencies and their assignments have been reported for isotopi-
Raman activities of the normal modes for the following linear molecules. Indicate cally pure )OOMoF6 in the gas phase [R. S. McDowell, R. J. Sherman, L. B.
the number of polarized Raman bands and the number of frequencies that should Asprey, and R. C. Kennedy, I. Chem~ Phys. 1975,62, 3974.):
be coincident between the two spectra. (a) CO2, (b) OCN-, (c) H-C=C-H,
(d) CI-C=C-H, (e) H-C-C-C=C-H. Raman (cm-l) Assignment Infrared (cm-l) Assignrnent
6.7 The nitrate ion in aqueous solution shows a tendency to associate with a variety
741 ± 0.8 (poI) 1479.4 ± 0.5 +
of metal cations (e.g., Ag ", Cu2+, Zn2+, Hg2+, Ca2+, AI3+, Ce3+, Th +).
4 VI VI V3

652.0 ± 0.5 V2 1386.4 ± 0.5 V2 + V3

Depending on concentration and cation, the association may involve direct ion
531 ± 3 2V4 913.1 ± 0.5 V2 + V4
pairing or pairing through one or more solvated water rnolecules. In dilute solu-
380 ± 3 )14 + V6 739.3 ± 0.5 V)
tions where such association is minimal and NO} has nearly its idealized D3h
317 ± 1 V5 262.7 ± 0.5 V4
sym~etry, four frequencies can be observed: 1400 cm -I (infrared, Raman),
233 ± 2 (poI) 2V6
1050 cm -I (Raman, polarized), 830 cm -1 (infrared), 720 cm -I (infrared, Raman).
200 Chapter 6 Vibrational Spectroscopy

(a) From the Raman bands assigned as 1/~ + 1/6 and 21/~, the frequency of the
fundamental lJ(, can be estirnated to be 117 cm - I. Why is no band reported
at this frequency in either the infrared or Raman spectrum?
CHAPTER 7
(b) The Raman band al 741.8 cm- I is nearly the same frequency as the infrared
band at 739.3 cm - I. How can we be certain that these bands are not from
the same normal mode?
(c) The data above show three Raman bands and three infrared bands assigned Transition Metal Complexes
lo various overtones and combinations. Show that each of these assignments
is plausible on the bases of Irequency, symmetry, and expected spectroscopic
activity.
(d) None of the overtones or combinations observed in the Rarnan spectrum is It is not our intention in this chapter to duplicate the kinds of presentations
observed in the infrared spectrum. On the basis of your results in part (c), is of transition metal chemistry that can be found in most standard advariced in-
this an expected result? organic chemistry texts. In particular, we will gloss aver most quantitative as-
(e) Estimates of the frequency of 1/(, come from the Raman data only. Is any pects of the subject and ignare almost completely the descriptive chemistry
combination of the type 1/i + 1/6 (i = 1,2,3,4,5) allowed in the infrared? If
of coordination compounds. Rather, our focus will be on the physical conse-
so, approximately what frequency would it have? Account for the absence of
quences that follow from the symmetry of transition metal complexes.
any such cornbination in the reported infrared spectrum.
Nonetheless, a certain amount of duplication with other treatments will be
unavoidable but should ensure that our examination of the symmetry aspects
of transition metal chemistry is fully appreciated. In particular, it will be nec-
essary to have had some prior exposure to Russell-Saunders coupling terms
far various equivalent d" configurations. Consequently, we will undertake a
brief review of the fundamental concepts and terminology before addressing
the symrnetry-induced effects. More detailed discussions of Russell-Saunders
terms can be found in most standard physical chemistry texts. *

7.1 Crystal Field Theory

In 1929 Hans Bethe published his classic paper on the splitting of terms in
crystals, which laid the foundation far crystal field theory' The work, in
German, is long and difficult, requiring a thorough understanding of group
theory and quantum mechanics. Little wonder, then, that few English-speak-
ing scientists of the time, with the notable exception of theoreticians such as
J. H. Van Vleck,* adopted this approach far interpreting the magnetic and
spectroscopic properties of transition metal complexes. Instead, the valence
bond (VB) approach, championed by Linus Pauling and others,' was the

*For example, see any of the following: P. Atkins, Physical Chemistry ; 5th ed., W. H. Freeman,
New York, 1994, pp. 451-456; R. A. Alberty and R. J. Silbey, Physica! Chemistry;John Wiley &
Sons, New York, 1992, pp. 370-378; G. M. Barrow, Physical Chemistry ; 6th ed., McGraw-Hill,
New York, 1996,pp. 495-502.
[H. Bethe, AnI!. Physik, 1929,3 [5], 135. An English translation of this paper, under the title
Splitting o] Terrns in Crystals, is available from Books on Demand, a Division of University
Microfilrns, lnternational, Ann Arbor, Michigan.
+1.H. Van Vleck, The Theory o] Electric and Magnetic Susceptibilities, Oxford University Press,
Oxford, England, 1932; Phys. Rev., 1932, 41,208; 1. Chem. Phys., 1935,3,803 and 807.
§L. Pauling, 1. Am. Chem. Soc., 1931,53, 1367; J. C. Siater, Phys. Rev. 1931,38, 1109. Also see
L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell University Press, lthaca, NY, 1960.

201