36

CHAPTER 2 - APPLICATIONS OF GROUP THEORY

2.1 How Group Theory Applies to a Variety of Chemical Problems

The classification of molecules according to their symmetry point groups, provides a
rigorous method for predicting optical activities. For a molecule to exhibit optical activity, it must
belong to a point group that does not possess an inversion center, mirror plane, or improper
rotation axis. The possibility of racemic mixtures must, of course, be considered. Molecules that
belong to point groups, such as C4 and other pure rotation groups, can exhibit optical activity if
resolved into one optical isomer.
Another helpful symmetry rule in the analysis of diastereomeric protons in NMR
spectroscopy is that chemically equivalent atoms (and hence protons with equivalent chemical
shifts) must be interchanged by a symmetry operation of the point group. For example, in Figure
2.1 the two protons Ha and Hb in structure A are equivalent because they are interchanged by the
A B

H H

CH3 CH3 H5 C6 CH3

C C

C C

Ha Hb Ha Hb

Cl Cl

Figure 2.1 Illustration of a structure, A, where Ha and

Hb are interchanged by a symmetry operation of the point
group. This would give rise to a single peak in the NMR
spectrum. In structure B, where no such operation exists,
Ha and Hb would give rise to separate peaks in the proton
NMR spectrum.
mirror plane operation, which contains the C-C bond in the plane of the paper and lies
perpendicular to the plane of the page. It is important to recognize that rotation around the C-C
single bond does not interchange Ha and Hb. The conformation produced by this bond rotation is
not equivalent to the original one. The Cl substituent now lies above the plane of the paper and the
 37

molecule resides in a different rotomeric configuration (eclipsed vs. the original staggered). Only
the mirror plane operation interchanges Ha and Hb to produce a configuration indistinguishable
from the original one. In structure B of Figure 2.1 the substitution of a phenyl group for a methyl
group destroys the mirror plane operation that interchanges Ha and Hb. Now Ha and Hb are no
longer equivalent and they give rise to separate peaks in the proton NMR spectrum. Further
examples will appear in Chapter 7 that show the power of this approach for the analysis of chemical
shift nonequivalence in complex structures.
The preceding examples concern straightforward conclusions derived from a consideration
of symmetry operations and equivalent configurations; however, the real power of group theoretical
methods results from their application to equivalent functions in a molecule. Just as group theory
can categorize equivalent atoms in a structure, it can also categorize equivalent functions. The
main applications concern electronic and vibrational wavefunctions in molecules. For example, the
two 1s atomic functions on hydrogen atoms Ha and Hb are equivalent in Figure 2.1 A. The two C-
H bond stretches (vibrational wavefunctions) to these atoms are also equivalent functions. Since all
of spectroscopy involves the transition between two states characterized by wavefunctions of one
kind or another, it is possible to apply group theory widely. This chapter describes how a set of n
equivalent functions can be rearranged into a set of n linear combinations that take advantage of
molecular point group symmetry. This requires knowledge about group representations. The payoff
will be that this permits the prediction of spectra, selection rules, and molecular orbital diagrams
without the need for detailed quantum mechanical calculations.

2.2 Matrix Representations of Symmetry Groups

^ acting on the point (x,y,z) are defined generally in eqn. 2.2.1.

Symmetry operations R
^
R(x,y,z) (x1, y 1, z 1) (2.2.1)
^
Because R preserves the size and shape of objects, it satisfies the requirements for a linear
operator shown in eqn 2.2.2 and 2.2.3. Therefore, it is natural to apply the matrix methods of linear
algebra in the description of symmetry operations.

^R(ax, ay, az) = aR(x,^ y, z)

(2.2.2)
^ (x + bx , y + by , z + bz ) = R
R ^ (x , y , z ) + b R
^ (x , y , z )
1 2 1 2 1 2 1 1 1 2 2 2 (2.2.3)

^ on a vector a = a -i + a -j + a -k ( -i , -j , -k are the usual unit vectors for a

The action of R x y z

^R(x , bx , y + by y + by ) = R(x^ , y , z ) + bR(x^ , y , z )

right-handed orthogonal coordinate system) can be represented as in eqn 2.2.4.

1 2 1 2, 3 3 1 1 1 2 2 2 (2.2.3)
 38

- ^-
b = Ra (2.2.4)
Because R is a linear operator, eqn 2.2.4 can be written as 2.2.5.
- - -
bxi + byj + bzk = axRi ^ - + a ^Rj- + a ^Rk
-
(2.2.5)
y z
- -
The length of b must also equal the length of a (˙ b˙ = ˙ a ˙ ) for a linear operator. The symmetry
^ -j and R
^ -i , R ^ -k are new unit vectors in three dimensional space. They can be
transformed vectors R
- - -
expressed as some linear combination of i , j , k , which are basis vectors for this space.

^- - -
Ri = r1 1i + r2 1j + r3 1-k

^-
Rj
- - -
= r1 2i + r2 2j + r3 2k (2.2.6)
^- = - -
Rk r1 3i + r2 3j + r3 3-k
Substituting in eqn 2.2.5 above and collecting terms yields eqn 2.2.7.
- - - - -
bx i + by j + bzk = (ax r1 1 + ay r1 2 + azr1 3)i + (ax r2 1 + ay r2 2 + azr2 3)j
(2.2.7)
-
+ (ax r3 1 + ay r3 2 + azr3 3)k
- - -
Equating coefficients of i , j , and k yields the set of equations of 2.2.8.
bx = axr11 + ayr12 + azr13
by = axr21 + ayr22 + azr23 (2.2.8)
bz = axr31 + ayr32 + azr33
- ^ a- can be written as shown in 2.2.9. Remember, to
In matrix notation, the set of equations b = R
multiply a matrix times a column vector one multiplies each matrix row times the column.

bx r11 r1 2 r1 3 ax

by = r21 r22 r23 ay (2.2.9)

bz r31 r3 2 r3 3 az

The 3 x 3 matrix is called the matrix representation of the linear transformation R.

Consider the specific example of a four-fold rotation around the z axis. The effect of this
operation on x,y,z is given by eqn 2.2.10.
^ (z) (x,y,z)
C 4 (-y,x,z) (2.2.10)
 39

A point also defines a vector from the origin of the coordinate system. The action of the
^ - -
counterclockwise C4(z) rotation on the vector a = (x,y,z) therefore yields b = (-y,x,z), which can be
pictured as follows:
y bx = -y = 0x + (-1)y + 0z
•
(-y,x,z) • (x,yz) by = x = 1x + 0y + 0z (2.2.11)
x
bz = z = 0x + 0y + 1z
Thus eqn 2.2.10 can be abbreviated in matrix form as 2.2.12.

-y 0 -1 0 x

x = 1 0 0 y (2.2.12)

z 0 0 1 z

The matrix form of the operator C4(z) is the matrix shown in eqn 2.2.13.

0 -1 0

C4(z) = 1 0 0 (2.2.13)

0 0 1

It can be shown that matrices representing symmetry operations are real and orthogonal. Therefore,
the transpose of matrix R gives the inverse matrix (R-1 = transpose of R). Recall that the transpose
of a matrix is constructed by interchanging corresponding elements across the diagonal of the
matrix (rij Æ rji). It is important to remember that the matrix for a coordinate axis transformation is
the inverse of the corresponding transformation for the point (x,y,z). For example, counterclockwise
rotation of the coordinate system by C4(z) leads is depicted below.

j i´

• •
i j´
The reason for the inverse relationship between the matrices of coordinate axes and points is easy to
visualize. Rotation of a coordinate system counterclockwise produces the same effect on a
 40

stationary point, from the reference frame of the coordinate system, as if the "stationary point" were
rotated clockwise (the inverse transformation).
Consider the matrix representations for common symmetry operations. Counterclockwise
rotation (Cn) about the z axis by angle a requires a computation of the rotated unit vectors i´ and j´
in terms of their projections on i and j. Simple trigonometry yields:
-
j ^ (z)i- - - -
- - C = i´ = i cos a + j sin a
j´ i´ n
^ (z)j- - - -
Cn = j´ = -i sin a + j cos a
-
i - - -
^ (z)k
C = k´ = k
n
^
Therefore we can express Cn(z), where a = 360/n, as in eqn 2.2.14

- -
i cos a sin a 0 i

^C - -
360/a (z) j = -sin a cos a 0 j (2.2.14)

- -
k 0 0 1 k

The transformation of the point or vector (x,y,z) uses the inverse of the transformation matrix for
the coordinate system, which is just the transpose (interchange elements off the diagonal) of the
preceding matrix.

x cos a -sin a 0 x

^C
360/a (z) y = sin a cos a 0 y (2.2.15)

z 0 0 1 z

For the corresponding operations S^ n, where the Sn axis lies along z, reflection in the x,y plane
inverts z (i.e. z' = -z). The matrix for corresponding S360/a operations are the same, except r33 =
-1. For sv in a plane containing z and making an angle b with the x axis, sv´ is related to sv(xz) by
the similarity transformation that involves Cb.
 41

sv ´

y
b

x (2.2.16)

^ -1 s(xz)
^sv ´ = C ^ ^C
b b

cos b -sin b 0 1 0 0 cos b sin b 0

sv ´(b) = sin b cos b 0 0 -1 0 -sin b cos b 0 (2.2.17)

0 0 1 0 0 1 0 0 1

cos b -sin b 0 cos b sin b 0

= sin b cos b 0 sin b -cos b 0 (2.2.18)

0 0 1 0 0 1
Ê (cos2 b - sin 2 b ) 2 cos b (sin b ) 0ˆ
Á 2sin b (cos b ) (sin b - cos b ) 0˜
2 2
(2.2.19 )
Á (cos2 b - sin2 b) 2 cos b (sin b) ˜0
Ë 0 0 1¯
= 2a = 2 sin a cos a2and
But sin 2a2 = cos2 a2 - sin2 a. (2.2.19)
sin bcos(cos b) sin b - cos2 bThis leads
0 to eqn 2.2.20, when the
mirror plane contains z and makes an angle b with the x axis.
0 0 1
cos 2b sin 2b 0

sv = sin 2b -cos 2b 0 (2.2.20)

0 0 1

2.3 Character Tables and Symmetry Group Representations

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^
We have defined a symmetry operation R acting on the point x, y, z and transforming the
point to some new equivalent location x',y',z' as in eqn 2.3.1.
^R(x,y,z)
(x´,y´,z´) currentpoint 192837465(2.3.1)
^
Applications to quantum mechanics require knowledge of the symmetry operation OR,
^
which acts on a wavefunction, y(x,y,z). The operator OR acts on a function so that the new function
^
O R y evaluated at x',y',z' has the same value as (x,y,z).
^ yR(x,y,z)
^
O R = O Ry(x´,y´,z´) = y(x,y,z) currentpoint 192837465 (2.3.2)
^
Left multiplying by OR-1 and transposing yields eqn 2.3.3.
^ -1yR(x,y,z) = y(x´,y´,z´)
O R currentpoint 192837465 (2.3.3)
This definition might seem backwards when compared with the definition of R; however, and the
^
opposite convention (i.e., ORyR(x,y,z) = y(x',y',z')) can be adopted if one is consistent. Because the
set of inverses of all the elements of a group give the group back, the convention makes no real
physical difference. We will use the convention of eqn 2.3.4-6, which can also be
^ y(x´,y´,z´) = y(x,y,z)
O R currentpoint 192837465 (2.3.4)
written as 2.3.5.
^ y(x´,y´,z´) =
^ -1x´,y´,z´)
Oy(R
R currentpoint 192837465 (2.3.5)
Since the primes are arbitrary, let q represent (x,y,z) and one can use the expression 2.3.6.
^ y(q)- = y(R-1q) -
OR currentpoint 192837465 (2.3.6)
This latter form is most useful in applications.
A symmetry group can be regarded as an n-dimensional function space. The behavior of a
^
general function y, under the operations of a group OR can be expressed as a combination of the
behavior of "basis functions" that span the possible behaviors of a function belonging to group G.
^
The group Cs (s in the yz plane) and the behavior of various functions f(x) with respect to
reflection illustrates this point.

^sx = -x antisymmetric fn or odd fn

^sx2 = (-x)2 = x2 symmetric fn or even fn
^scos(x) = cos(-x) = cos(x) symmetric fn
^s(x2 + x) = x2 - x linear combination of a symmetric and antisymmetric fn
^s(x4 + x3) = x4 - x3 linear combination of a symmetric and antisymmetric fn

A function is symmetric if it is unchanged when acted on by ^s and antisymmetric if the function

goes into minus itself. The properties of symmetry and antisymmetry with respect to s define the
fundamental behavior of functions in the Cs group. All linear functions can be decomposed into a
 43

linear sum of symmetric and antisymmetric parts. A character table for Cs , which summarizes
these conclusions is shown below.

Cs E s Cs E s
____________________ _________________
symm 1 1 A´ 1 1
antisymm 1 -1 A´´ 1 -1
The symmetric and antisymmetric types of functions are more conventionally denoted A´ and A´´.
366 40 1296 20 20 chemdict begin SP
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fundamental types of functions one needs to describe symmetry behavior in the two-dimensional
group Cs . The characters ±1 show how operations of the group change functions that transform
like these irreducible representations. For example, the functions x and x3 are A´´ and cos x or x2
are A´ in the Cs point group. A linear function, such as x + x2 + x3, can be decomposed into A´ +
2A´´ irreducible parts. This intuitive development can be formalized.
Earlier we showed that matrices could be used to represent symmetry operators of a group.
It follows that matrix representations multiply just like the symmetry group operations, and form a
group isomorphic to the point group of symmetry operations. In fact, any set of square matrices
that multiply like the elements of a group form a representation for that group. The order of the
matrices defines the dimension of the representation. The correspondence between matrices and
symmetry operations need not be one-to-one. A matrix can correspond to more than one group
element. For example, let the 1 x 1 matrix (1) = all the elements of a group. Thus for Cs .
E s and E x s
(1) (1) (1) x (1) = (1)
This trivial one-dimensional representation satisfies all the requirements for a group and is a valid
group representation. The many to less correspondence between the group elements and matrices is
called a homomorphism, and the matrix representation is termed unfaithful. When a one-one
correspondence (isomorphism) exists, the representation is called faithful.
When dealing with matrices, it is convenient to define the trace or character of a matrix R
that is the sum of the diagonal elements in eqn 2.3.7.

Tr(R) = Sa i i
i currentpoint 192837465 (2.3.7)
For symmetry operator matrices that represent a group isomorphically R2-1R1R2 defines a similarity
transformation of coordinates. From matrix theory it can be shown that R2-1R1R2 defines R1 with
respect to a new set of basis vectors. In other words, the operation is the same but just defined in
another basis. This makes sense, since the equivalent symmetry operations in a conjugate class
 44

consist of similar kinds of operations that differ only in spatial orientation. The trace or character
of a matrix does not change after a similarity transformation. With this aside, return to the
problem of representations.
1 0 0 0

0 -1 0 0

0 0 1 -1

0 0 -1 -1
1 0 0 0

0 +1 0 0

0 0 1 1

0 0 1 1
For a group of order n, it is possible to find a set of n matrices that faithfully represent the
group. By similarity transformations, the set of matrices can be arranged in the most reduced form
(block diagonal form), as shown above. The number of elements in the submatricies for each
operation will equal the order of the group. The submatrices are themselves unfaithful
representations of the group. For most purposes, enough information is contained in the trace or
character of these matrix representations. Furthermore, group elements belonging to a class can be
grouped together because they have identical characters. The character table for the C3 v group
has the form shown below.

^ ^ (z)
C3 v E 2C3 3sv
A1 1 1 1 z, z 2 , x 2 + y2

A2 1 1 -1 Rz

E 2 -1 0 (x,y), (R x ,R y ), (x 2 -y2 , xy), (xz, yz)

The irreducible representations named A1, A2, and E are the fundamental ways that a function can
be classified in the C3 v point group. This example provides some new complexities as compared to
Cs . The simultaneous effect of C3 and s operations influences the classification of symmetry type.
Both the A1 and A2 representations are unchanged (i.e., symmetric) under C3 or C32 rotations.
While A1 also does not change under a s operation, the A2 representation is antisymmetric. For the
two dimensional E representation, the characters alone do not tell us about symmetric or
antisymmetric behavior, because they represent the composite trace of 2 x 2 matrices. The rightmost
column provides transformation properties for several functions relevant to physical problems. The
x, y, and z coordinates behave just like atomic px, py, and pz orbitals or the x, y, and z components
 45

of the electric dipole moment operator, so far as their symmetry properties are concerned. These
behaviors can be derived using methods described in section 2.5 and 2.6.
The following theorems hold for the group representations:
1) The number of classes in the group = Number of unique irreducible representations
^ th operator of the
2) Let Gi = ith irreducible representation and let XR(Gi) = the character for the R
representation Gi. Then
2
S X ^E(Gi) = order of the group = g
i
This means that the number of elements contained in the matrix representations equals the order of
the group.
2 ^ so all elements
3) S XR^(Gi ) = order of the group for any Gi (note S includes sum over R
R
in each class must be included)
above Gi should be Gi!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

4) SXR^(Gi )X ^R(Gj ) = gdi j (i.e., rows are orthogonal)

R
2
5) If S XR
^( Gi) = g, then Gi irreducible repres
R then G i is an irreducible

representation.
6) The columns of the character table are orthogonal and normalized to g/Nk (Nk = number of
elements in the class for the k'th column of the table).
Consider the application of these theorems to cyclic groups. For C5 , the five elements can be
written as b, b2, b3, b4, and b5 = e. By application of similarity transforms, one can show that each
element belongs to its own class. Therefore by theorems 1 and 2 there will be 5 one-dimensional
irreducible representations. From Lagrange's Theorem (section 1.2) the order of the elements of the
group must be 1 or 5. Since the element of order 1 is ^e , the others must obey the relation.
Xb5(Gj) = 1
c = e2pi(n/g) n = 1,2,3 - - -, g
This equation defines the g th roots of unity, since cg[G(b)] = e2pi = 1. These roots are abbreviated
as e, e2, - - -, eg (e = e2πi/g). For the specific case of C5 , where e = e2pi/5:
 46

C5 C5 C52 C53 C54 C55

______________________________________________________________
G1 e e2 e3 e4 e5

G2 e2 e4 e6 e8 e10

G3 e3 e6 e9 e12 e15

G4 e4 e8 e12 e16 e20

G5 e5 e10 e15 e20 e25

Next use the fact that:
e3 = e2pi3/5 = e2pi(-2/5) = (e2pi(2/5))* = e2* and
en5+j = ej
Here * denotes the complex conjugate, and we recognize that rotation by (+3/5)2p and (-2/5)2p in
the complex plane are equivalent. Continuing the process for the group C5 yields the character
table:
C5 E C5 C52 C53 C54

G5 A 1 1 1 1 1
G1 1 e e2 e2* e*
E1
G4 1 e* e2* e2 e
G2 1 e2 e* e e2*
E2
G3 1 e2* e e* e2

The reason for pairing G1, G4 as E1 and G2, G3 as E2 is that they are complex conjugate
pairs. For most physical problems involving real functions, the complex conjugate pairs are
effectively degenerate (not so for magnetic problems like the Zeeman effect where y ~eimf). The
complex conjugate pairs can be added [recall eia = cos a + i sin a and e-ia = cosa -i(sina) =
(eia)*] and then only the real (cosq) part is retained. This yields a C5 character table that is
sufficient for solving problems with non-imaginary functions.
 47

C5 E C5 C5 2 C5 3 C5 4
A 1 1 1 1 1
2p 4p 4p 2p
G1 + G4 = E1 2 2cos 2cos 2cos 2cos
5 5 5 5

2 4p 2p 2p 4p
G2 + G3 = E2 2cos 2cos 2cos 2cos
5 5 5 5

2.4 Symbols for Irreducible Representations

The Bethe nomenclature uses G1, G2, G3 - - - to specify irreducible group representations.
This notation is still used for double groups, as discussed in a later chapter. Otherwise the Mulliken
notation is usually employed by chemists. For one-dimensional irreducible representations, c(E) =
1. One dimensional representations are called A if symmetric with rotation around the principal
axis of symmetry, or B if antisymmetric with rotation around the principal rotation axis of the
group . Subscripts 1 and 2 denote symmetry or antisymmetry with respect to a ^ C2, or a sv if no
^ C2 exists. Primes and double primes specify symmetry or antisymmetry with respect to sh. In
groups that contain an inversion center, g or u subscripts denote even (g) or odd (u) behavior
with respect to inversion. Two-dimensional irreducible representations have c(E) = 2 and are
called E. Three-dimensional irreducible representations, for which c(E) = 3, are named T. For
one-dimensional irreducible representations, the character is the matrix and +1 denotes symmetry
with respect to a given operation, while a character of -1 means antisymmetry.
The totally symmetric representation is conventionally the first A representation in every
character table and all of its characters are 1. A function with this symmetry possesses the full
symmetry of the point group. All the other representations are called non-totally symmetric
representations. They represent functions of lower symmetry, since a character ≠ 1 means the
function does not go into itself on application of that symmetry operation. Character tables for the
important point groups are collected in Appendix A of this chapter.

2.5 Decomposing Reducible Representations - The Great Orthogonality Theorem.

Given a set of characters XR(Gi) for some representation, Gi, of a group, it is desirable to
find out how to reduce the representation to a sum of irreducible representations. The answer is
^ (G) we want to find out G = aGi +
provided by the great orthogonality theorem. That is, given XR
bGj + . . . . The number of times the irreducible representation Gi of the group is contained in
G may be calculated by the formula:
a
Gi = 1/g S X R^* (Gi) X R^ (G) (aGi = the number of times the Gi representations
R
occurs in G, g = order of group)
 48

For example the representation

E 2C3 3sv
6 0 0
in C3 v reduces to A1 + A2 + 2E. The calculation proceeds as follows:
aA1 = 1/6 {1(6) + 1(0)2 + 1(0)3} = 1
aA2 = 1/6 {1(6) + 1(0)2 - 1(0)3} = 1
aE= 1/6 {2(6) + -1 (0)2 + 0(0)3} = 2
^ operations in the same
Notice that because the sum occurs over all symmetry operations, the 2 C 3
class and the 3 equivalent sv must be included explicitly in the calculation.

2.6 The O-H Stretches of Water: Understanding Irreducible Representations

Significance of Irreducible Representations as Basis Sets for Chemical Problems. Suppose
there exists a set of linearly independent functions f1, f2, f3, - - fn. Consider a symmetry operation,
O^ , that permutes the set of functions, or mixes them with one another to form a new linearly
R
independent set of functions with dimension n. The set of matrices for O ^ form a representation of
R
the point group.

.
f1
. .
.
.
= a fi +b fj + . . .
^q
R .
reorg
. .
. .
fn .
OR above!!!!!!!!!
Any set of n independent equivalent functions that are transformed into linear combinations of one
another by the symmetry operations of the group form a basis for an n-dimensional
representation of the group. The trace of the representation matrix yields characters that allow the
decomposition of the n-dimensional representation into a sum of irreducible representations. This
procedure permits a classification of electronic, vibrational, rotational or spin wave-functions of a
molecule transform in terms of the irreducible representations of the molecular point group. The
degree of degeneracy of a molecular energy level equals the dimension of the irreducible
representation to which its wavefunction belongs.
Consider what group theory has to say about a simple problem, the O-H stretching
vibrations in the water molecule. The vibrational wavefunctions are classified according to the
 49

various irreducible representations of the molecular symmetry group for water. A naive approach
might suggest that both O-H bonds are equivalent, and therefore both would occur at the same
stretching frequency in the infrared spectrum. This simple view ignores the coupling of the two
vibrations. Stretching of one O-H bond changes the degree of difficulty of stretching the other
bond. Group theory requires that two equivalent functions form the basis for a two-dimensional
^
group representation. Refer back to Figures 1.4 and 1.5, which show that ^s(xz) and C2 interchange
the two O-H bonds, while ^s(yz) leaves them unchanged. Each bond stretch can be depicted by a
double headed arrow centered in each bond. Therefore the symmetry operations affect the two O-H
bonds as follows:

^ O-Ha O-Hb
C 2 =
O-Hb O-Ha

^s(xz) O-Ha O-Hb

=
O-Hb O-Ha

^s(yz) O-Ha O-Ha

=
O-Hb O-Hb

The matrices for this two-dimensional representation are:

^E ^
C ^s(xz) ^s(yz)
2
10 01 01 10
01 10 10 01

The characters for this representation, denoted GO-H, are obtained by summing the diagonal
elements and can be compared with the C2v character table shown below.
 50

C2 v E C2(z) sv(xz) sv(yz)

__________________________________________
A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1
GO-H 2 0 0 2
Thus G O-H is a reducible representation, which by inspection (or the formula of section 2.5)
consists of A1 + B2. Because there are no degenerate representations in C2 v symmetry, the two O-
H vibrational wavefunctions cannot be degenerate. The water molecule should show two different
O-H stretching vibrations by infrared spectroscopy (more about selection rules later). This
prediction of group theory is borne out experimentally, since two such vibrations occur at 3652 cm-
1 and 3756 cm-1 in the gas-phase IR spectrum of water. The C2 v character table requires that all

wavefunctions of the water molecule be nondegenerate. Any degeneracy that might occur must be
by sheer coincidence and is termed accidental degeneracy.
Before proceeding, there are two significant observations. First, in computing the character
for the two O-H stretches a value of 1 occurs along the diagonal for each bond that goes into itself.
Off-diagonal elements of the matrices need not be considered, when calculating the characters.
Second, if the coordinate system were selected so the water molecule was in the xz plane, then the
characters for the O-H stretches would have been (2 0 2 0) = A1 + B1. Either description of the O-
H stretches as A1 + B1 or A1 + B2 is correct, they merely correspond to a different choice of
coordinates. Two scientists describing the IR spectrum of water could appear to be in disagreement,
when the difference is merely one of coordinate axes. This illustrates the importance of clarifying
the coordinate system choice (and being consistent) to avoid confusion. Neither OHa nor OHb
alone behave as an irreducible representation in the C2 v point group.
Now consider a more complex case where mixing of functions occurs. For the functions x
and y in C 3 v symmetry, the C3 operation mixes the two coordinates according to eqn 2.2.15 (a
specific case of the general rotation matrix derived previously). Because of this mixing, both x and
y must be considered together as a two-dimensional representation.

E C3 (z) sv
1 0 cos 120 -sin 120 1 0
sin 120 cos 120 0 -1 (2.2.15)
0 1
Computation of the sv matrix takes advantage of the option that the orientation of the x and y axes
are arbitrary, as long as they lie perpendicular to z. The calculation is simplified with the assumption
that sv lies in the xz plane. By reference to eqn 2.2.20, it is easy to see that the trace of the matrix
would indeed be zero regardless of the value of b (i.e., the orientation of ^sv with respect to the x
 51

axis). Furthermore, the character is the same for equivalent elements in a class, and so only one of
^
the 2 C3 and 3 ^sv operations need be considered. The trace of these three matrices (2 -1 0) verifies
that x and y together form a basis for the E representation of C3 v.