Introduction to group theory

Upendra Harbola
Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore
The concept of symmetries is important in physics and chemistry. In this course we will learn
how to use symmetry arguments to gain insight into the eigenspectrum of quantum systems. Most
systems in the nature have certain symmetries (they may be obvious in some systems and not-soobvious in others). These symmetries may be in real space, time space or in some abstract space,
such as energy space. In this course we will be focused only on symmetries in real space. The set
of symmetries form a group. We will formulate the group theory to exploit these symmetry groups
to learn about the quantum system.

2
CHAPTER 1: FORMAL DEVELOPMENT

The stationary states |i corresponding to an

Consider a quantum system described by the Hamiltonian H.
eigenvalue E satisfy eigenvalue equation,

H|i
= E|i.

(1)

Let us suppose that the system possesses a set of symmetries in real space. Then a collection of this system each at
dierent symmetry states would be indistinguishable. Clearly, they all must be described by the same Hamiltonian.
performs a certain symmetry operation, then O
must commute with H.

Now if an operator O
H
=H
= O.

O
We apply this transformation to the eigenvalue equation (1). This gives,
H|i

O|i

O
=H
= E O|i.

(2)

Thus O|i
is also an eigenstate of the Hamiltonian with the same eigenvalue, E. Let O|i
= |0 i. We rst assume
0
that this state is non-degenerate. Then i is proportional to i. That is the two states dier by a phase factor.
Thus 0 i and i have the same functional form. Here we are concerned only with the coordinate transformations.
That is each symmetry operation involves some kind of coordinate transformation. For simplicity, here we assume
that this transformation is such that, when applied twice, it brings the system back to its original conguration, that
is,
O|i

O
= |i.

(3)

Thus nondegenrate eigenfuncThis implies that the function |i has a denite parity 1 under the transformation O.

tions of H are either symmetric or antisymmetric to symmetry operations. We therefore have a way to catagorize all
eigenfunctions in terms of their parity with respect to various symmetry operations of Hamiltonian. This formulation
of classication based on the parity with respect to symmetry operations is called group theory.
The criteria that a symmetry operaion leaves the Hamiltonian unchanged and corresponds to a dinite parity of
eigenfunctions leads to two types of symmetry operations.
1). Point symmetry transformations and 2). permutation operations that interchanges two identical particles.
All point symmetry operations must leave at least one point unaected which is the point where the three axes
meet. Rotations and reections about a plane are the point symmetry operations.
Group algebra
The symmetry operations of a system form a group. A group is a collection of elements that are interconnected
according to a rule. A complete group must satisfy the following properties.
1. The combination of any two elements of the group according to a prescribed method must be an element of the
same group.
2. One element in the group is such that, when combined with an element, it leaves the element of the group
unchanged. This element is called the identity of the group.
3. Any element must satisfy the assosiative law of combination with respect to other elements of the group.
4. Every element of the group must possess a reciprocal, which is also an element in the group.
Order of a group is the number of elements in the group. Let us consider a group G3 = {A, B, C} with three
elements. If this is a complete group under ordinary multiplication rules, then according to the denition of a group,
AB must be equal to either A or B or C. If AB = A, then B is the identity of the group and BC = C, BB = B.
According to the associative law, A(BC) = (AB)C. (In general AB 6= BA).
[* Show that under ordinary addition rule, the set of integers G = { , 1, 0, 1, } forms a group.
*Show that under ordinary multiplication rule the set {1, 1, i, i} is a complete group.]
Abelian group: If all elements of a group commute among themselves, the group is known as Abelian.
Cyclic group: A group whose elements can be expressed as some integer power (less than or equal to the order of
the group) of a single element of the group, is called a cyclic group. Note that all cyclic groups of order n are identical.
[* Show that all cyclic groups are abelian.]

3
A group of order n, Gn , will have n2 combinations. We can arrange these combinations in the form of an n n
matrix. This matrix is called the group table. The importance of a group table is to determine whether a set forms
a complete group or not. All rows and columns in a group table are distinct. Any element in the group table can
appear only once in a row and a column.
For a group G4 = {I, A, B, C}, there are two possible group tables:

(1)

G4

I
= A
B
C

I
I
A
B
C

A
A
B
C
I

B
B
C
I
A

C
C
I
A
B

(2)

G4

I
= A
B
C

I
I
A
B
C

A
A
I
C
B

B
B
C
I
A

C
C
B
A
I

(1)

(4)

(2)

These represent two dierent groups of order 4. In the group G4 , the element B is its own inverse while in G4 , all
(1)
(2)
elements are their own inverses. Note that group G4 is cyclic (and hence abelian) while G4 is abelian but not cyclic.
In any group, some integer power of each element must give the identity element of the group. This integer power
(1)
is called the order of the element. In the group G4 above, the order of A is 4, same as the group order. While
(2)
in G4 , the order of A is 2 (all elements have the smme order in this group). The group order is always an integer
multiple of the order or each elements.
[* Show that if the order of any element in a group is the same as the order of the group, then the group is cyclic.]
Some elements with a group can form a complete group independently under the same composition rule as for the
(2)
group. The collection of such elements form a subgroup of the group. In the group G4 above, the set G2 = {I, A}
forms a complete set, so do G2 = {I, B} and G2 = {I, C}. Thus {I, A}, {I, B}, and {I, C} all are subsets (subgroup)
of order 2 of group G4 of order 4. G1 = {I} is always a subgroup of every group. Thus each group has atleast one
subgroup of order 1 formed by the identity element.
Lagrange Theorem: Order of any subgroup (h) of a group must be an integer multiple of of the order (n) of the
group.
Proof: Let {ai }, i = 1, 2, h forms a subgroup of order h of a group pf order n > h. Let b
/ ai , then bai Gn
and bai
/ {ai }. Since bai generates a set of distinct h elements, the set G2h = {ai , bai } has 2h elements and also
forms a subgroup of Gn . We can again choose an element c
/ G2h and c Gn , to construct a subgroup of order 3h,
G3h = {ai , bai , cai }. We can repeat this process until we reach k steps when hk = n. That is n/h = k, an integer.
**Since the identity element, which can be obtained as an integer power of any element of a group, forms a subgroup
of the group, as a corollary of Lagrange theorem, it turns out that the order of any element of a group must therefore
be an integer divisor of the order of the group. This can also be shown as follows.
Let element A Gn and the order of A is k n, that is Ak = I, the identity element in Gn . Let k = nq where
q N0 . Then (A)nq = I = (An )q = (Ank )q . This implies either q(n k) = k, that is k = qn/(1 + q), that is k is
an integer divisor of n.
[* Show that there is only one group of prime order.
Hint: If k is the order of an element of a group Gn , then n = kh, where h is an integer. Since n is a prime, h must
be either 1 or n. Thus order of any element is either 1 or n. Since only identity element can have order 1, all other
elements have order n. The group is therefore cyclic.]
Let Gh = {I, A1 , , Ah } be a subgroup of a group Gn , n > h and let an element g Gn but g
/ Gh , then the set
gGh and Gh g are called the left and the right cosets of Gh . A coset may not be a subgroup. For example, in the
(2)
left and right cosets of the subgroup {I, A} of group G4 above are
I{I, A} = {I, A}, A{I, A} = {I, A}, B{I, A} = {B, C}, C{I, A} = {B, C}
{I, A}I = {I, A}, {I, A}A = {I, A}, {I, A}B = {B, C}, {I, A}C = {B, C}.
We note that in this case, the left and right cosets of {I, A} are the same. Such a subgroup is called a self-conjugate
(2)
set. Therefore {I, A} is a self-conjugate subgroup of G4 . The disctinct cosets of this self-conjugate subgroup are

4
{I, A} and {B, C}. Note that the element-by-element multiplication of the two cosets gives another coset. Thus
{I, A}{I, A} = {I, A}, {I, A}{B, C} = {B, C}
{B, C}{I, A} = {B, C}, {B, C}{B, C} = {I, A}.
If we assign a mapping {I} {I, A} and {A} {B, C}, then the group {I, A} is known as the factor group of
the subgroup {I, A}. The composition table of this factor group is
I A
I I A
A A I.

(5)

(2)

Comparing this compposition table with the composition table of the group G4 , we nd that the structure of the
table remains the same. Thus the factor group of a self-conjugate group gives a mapping on to the group. In this
case this mapping ({I} {I, A} and {A} {B, C}) gives a homomorphic mapping since the dimensions of the
composition table is reduced, that is mapping is not one-to-one, that is, some of the properties of the group may be
lost. In this case, the factor group is cyclic but the original group is not. Note that in the mapping to the factor group,
elements I and A are arbitrary. For example, we could choose {I, A} {1, 1}, which forms the same composition
table under ordinary multiplication (they can be understood as one-dimensional matrices). Thus under this mapping
the elements (I, A) belong to a property denoted by 1 while elements (B, C) have the property of element 1. The
homomorphic mapping is not reversible due to the reduction in the group space (order).
Conjugate elements: Any two elements A and B of a group Gn are said to be conjugate to each other if, for
C Gn ,
C 1 AC = B,

= AC = CB.

Thus two conjugate elements are related via a similarity transformation. The total number of conjugate elements in
a group is the class of the group.

5
CHAPTER 2: POINT SYMMETRY OPERATIONS

All operations under which a system is transformed into physically equivalent congurations are called symmetry
operations.
1. Rotation: If a rotation about an axis by an angle 2/n, n, 1, 2, , brings the system to an equivalent
conguration, the axis is called a proper axis of rotation and the operation is denoted by Cn . Clearly n such rotations
will bring the system to its original conguration. Therefore, (Cn )n = Cnn = I, the identity operation. By convention,
the axis with maximum symmetry is taken as z axis.
Consider a three atom molecule where each atom is located at the vertices of an equilateral triangle. We consider
all atoms to be of the same type. It then has C3 symmetry around the z-axis or z axiz is the C3 axis. C32 is also
a symmetry operation becasue it also brings the system to an equivalent conguration. Therfore z axis is a 2-fold
symmetry axis also. Of course, C33 = I. If we consider only a 2-dimensional trangle, then these are the only possible
rotational symmetries. In a 3-D case, we have three more C2 axes passing through the vertices of the triangle and
meeting the z-axis at the center of the triangle. Note that under all these rotations, this point at the center remains
unaected. The existance of a C3 axis and a perpandicular C2 axis implies the existance of two more C2 axis since
C3 operation rotates the C2 axis as well.
A square planar molecule has one C4 axis (which is also C2 axis). There are four other C2 axes.
[* Find out all the rotation axes in a cube.]
2. Reflection planes: Reection of all points through a mirror plane placed somewhere in the system is a symmetry
operation if such a transformaton brings the system to an equivalent conguration. The conventional symbol for this
operation is . Reection through the plane xy is denoted (xy). Planes containing the principle axis (axis with
highest symmetry, z-axis) are denoted v . All planes parpendicular to v are denoted h (for horizontal).
The triangular molecule AB3 considered above has three v planes and one h (for 3-D case). A square planar
molecule has four v planes (two containing diagonal C2 axis are actually denoted as d , for diagonal) and one h
plane. Since applying operation through a plane brings back the system to its original conguration, 2 = I.
** A linear molecule has innite number of symmetry planes.
3. Inversion symmetry: If, with respect to an origin dened on the system, changing ~r ~r for each point on
the system, we can obtain an equivalent conguration, then the origin point is called the center of inversion and the
system is said to possess inversion symmetry. If an molecule has one atom of dierent type and the molecule has
inversion symmetry then this atom must dene the center of inversion. Clearly, if there are two or more nonequivalent
atoms in a molecule, it can not have inversion symmetry. Inversion operation is denoted by i. Then i2 = I.
** A molecule with inversion symmetry has no net dipole moment.
Improper rotation: If the system can be brought into an equivalent conguration by performing a rotation about
an axis and a subsequent reection through a plane perpandicular to the rotation axis, then the axis is called the axis
of improper axis and the system is said to posses an improper axis or improper rotation symmetry. This operation is
denoted by Sn = h0 Cn . The molecule C2 H6 has S6 symmetry axis.
If we apply Sn operation even number of times, the eect of reection cancels out since 2m = I. Then Snm = Cnm
if m is even. Thus for even n, Snn = I. Let us look at S2 . This requires one C2 and a operation. This is clear that
this transformation performs an operation under which ~r ~r. Thus S2 = i.
S6 , S62 , S63 , S64 , S65 , S66 S6 , C3 , i, C32 , S65 , I.
** Thus existance of S6 implies the existance of C3 axis. In general if n is even, existance of Sn symmetry implies
the existance of Cn/2 symmtery.
For odd n, Snn = . Thus existance of Sn implies the independent existance of and Cn symmetries. Sn with odd n
generates 2n distinct operations.
[* S5 , S52 , S53 , S54 , S55 , S56 , S57 , S58 , S59 , S510 ?
22
What is S11
?]

6
** For a molecule to possess optical isomerism, the corresponding symmetry group must not contain an improper
axis. Since S2 = i and S1 = . Thus the molecule must not contain a point of inversion and a plane of reection.
The group of symmetry elements of H2 O (C2v point group): G4 = {I, C2 , v , v0 }.
The group of symmetry elements of N H3 (C3v point group): G6 = {I, C3 , C32 , v , v0 , v00 }.
Composition table for C2v point group:
For C2v group we have, G4 = {I, C2 , v , v0 }. The C2 axis is along the z-axis. The two reection planes are
mutually orthogonal and contain the C2 axis. A C2 operation transforms the x and y corrdinates to x and y
coordinates, keeping the z coordinate unchanged. Thus in the basis of coordinates of a point, (x, y, z), the matrix
representation for C2 operator is,

1 0 0

C2 = 0 1 0 .
(6)
0 0 1
Similarly, a reection through v plane ( y z plane) makes the transformation x x, y y, z z, and v0 plane
(x z plane) changes x x, y y, z z. Thus both these operations have the following representations,

1 0 0
1 0 0

v (yz) = 0 1 0 ,
v (xz) = 0 1 0 .
(7)
0 0 1
0 0 1
We can then check that, C22 = 2 (yz) = 2 (xz) = I, C2 (yz) = (xz) and C2 (xz) = (yz). Thus the composition
table is given by,

C2v =

I
C2 (yz) (xz)
I
I
C2 (yz) (xz)
C2
C2
I (xz) (yz)
(yz) (yz) (xz) I
C2
(xz) (xz) (yz) C2
I

(8)

Thus each operation is its own inverse and we do not have any conjugate elements, that is C21 (xz)C2 = (xz), etc.,
and therefore each element has a distinct class. Thus class of the group C2v is four, same as order of the group. Note
that the trace of each operation in this representation is distinct.
** All conjugate elements in a group have the same trace.
** Trace of a matrix is independent of the representation.
Suppose a symmetry plane v () (it contains z-axis) is such that it makes an angle from the x-axis. In order to
perform the reection operation through this plane, we need to know its matrix representation. This can be done by
making a unitary transformation of the operator (xz) (or (yz)) about the z-axis. Thus v () = Mz ()(xz)Mz (),
where operator Mz () rotates the coordinate system around the z-axis by angle . Thus we get

cos2 sin2 0

v () = sin2 cos2 0
(9)
0
0
1
[* How many conjugate sugbgroups does the point group C2v have? Find out all their left and right cosets.
* Construct the composition table for the C3v point group and nd its class. How many conjugate groups are there
in this group?
* Find the composition table for a planer AB4 molecule and determine the number of classes it has.]
Note that any representation of symmetry matrices can be brought into a unitary form by similarity transformations,
and since similarity transformations preserve the composition table of a group, the group representation also preserves
the composition of group table and can always be assumed unitary.

7
CHAPTER 3: GROUP REPRESENTATION

Let Gn = {I, A1 , A2 , , An1 } and Gm = {I, B1 , B2 , , Bm1 } be two groups. If there is a mapping f between
the elements of two groups which preserves their composition table. Thus A1 = f (B1 ) and A2 = f (B2 ), etc. Then,
f (B1 B2 ) = f (B1 )f (B2 ) = A1 A2 .
In this case if the order of two groups is the same then the mapping is isomporphic and the two groups are called
isomorphis group. If m 6= n, then there is a many-to-one correspondance between the two groups and the two groups
are called homomorphic.
Example: The C3v point group G6 = {I, C3 , C32 , v , v0 , v00 } is isomorphic to the permutation group of an equilateral triangle. Since operations in both the groups, permutation in equilateral triangle and the symmetries of a
C3v point group can be represented by a common set of matrices where each matric corresponds only to exactly one
operation in either groups. Thus there is one-to-one correspondence between the two groups.
Next consider C1h = Cs point group, G2 = {I, h }. This is homomorphic to the C3v point group. This can be seen
by comparing the composition table for the two groups and we nd that the following correspondance exists between
the two: {I, C3 , C32 } {I} and {v , v0 , v00 } {h }. Thus the two groups are homomorphic onto each other.
[* Find the mapping and correspondance between C3v , S2 = {I, i} and Cs = {I, h } groups and show the correspondance between the elements.]
A symmetry group is either isomorphic or homomorphic to a group of matrices. The elements of the matrix
group are said to form a representation of symmetry group. Thus representation of a group consists in nding a
group of matrices that maps onto the symmetry group. This mapping may be isomorphis or homomorphic. If the
mapping is isomorphic (both grous are of the same order) then the representation is said to be faithful, otherwise the
representation is unfaithful. The group of one-dimensional matrices {1, 1} forms a faithful representation for the
point group Cs = {I, } while this is unfaithful for the point group C2v .
[* Show that there are three 2-dimensional representations for the point group C2v and only one of them is faithful.]
Thus there are innite number of possibilities for the representation of a symmetry group. However we are interested
only in the inequivalent representations such that one can not be obtained from the other by some transformation.
Let Gn = {I, A1 , A2 , , An1 } be a group and we nd two representations X = {X(I), X(A1 ) , X(An1 )}
and Y = {Y (I), Y (A1 ) , Y (An1 )}, which may be of dierent dimensions, for the group. Then if Ai Aj = Ak ,
X(Ai )X(Aj ) = X(Ak ) and Y (Ai )Y (Aj ) = Y (Ak ). We can now form a block diagonal matrices,
(
)
(
) (
)
X(I) 0
X(A1 )
0
X(A2 )
0
,
(10)
,
, etc.
0 Y (I)
0
Y (A1 )
0
Y (A2 )
Then these matrices also form a representation for the group. However this new representation is not unique, it is
clear that it is a combination of two dierent representations. This is obvious since the representation is in blockdiagonal form. However, we can make a similarity transformation of this representation using an orthogonal matrix,
Z = S 1 XS, this will give us a non block-diagonal representation, but it will still satisfy the composition table of the
group and thus a valid representation. But this transformed representation is exactly the same as before, hence last
two representations are equivalent to representation X and Y .
Thus if representation of a group can be brought into a block-diagonal form by a similarity transformation performed
on it, the representation is called irreducible, otherwise it is reducible. The representation Z above is thus reducible.
Thus reducible representations are the basis components from which all reducible representations can be obtained. In
order to nd whether a given representation is reducible or irreducible, in general it is a very tedius task to determine
wheteher there exists a matrix which simultaneously block-diangonalizes the representations for all elements of a
group. Thus in order to simplify things, we need to state few theorems, including the Great Orthogonality Theorem
(GOT), which is the fundamental theorem of teh group theory.
Schulers first Theorem: A matrix that commutes with every matrix of an irreducible representation is a constant
multiple of the unit matrix. If there is a non-constant matrix that commutes with every representation of the group,
then the representation is reducible.

8
Proof: Let {A1 , A2 , , An } be a representation of a group Gn . Let M be a matrix which commutes with all

matrices Ai in the representation; M Ai = Ai M . This implies that A1

i M = M Ai . Thus M commutes with
1

Ai , and hence with Ai . We can for a hermitian matrix H = M + M . Then H also commutes with Ai . Since H
is hermitian, we can nd a unitary matrix U which diagonalizes the matrix H, that is, U 1 HU = D, where D is a
diagonal matrix. Then we have,
U 1 Ai HU = Ai D = DAi , whereAi = U 1 Ai U.

(11)

Taking the matrix element (m, n), we get (Ai )mn (Dmm Dnn ) = 0. This shows that,
I.) If all the elements of diagonal matrix D are distinct, that is D has no degeneracy, all the o diagonal elements of
Ai are zero, that is Ai are diagonal matrices and hence represent reducible representation of one-dimensional of the
group Gn .
II.) If all the elements of D are identical, that is D is proportional to the unit matrix, then M , which commutes with
all matrices Ai , is also proportional to the unit matrix. In this case, Ai forms an irreducible representation of Gn .
Thus if Ai is irreducible representation, then only matrix that commutes with all the matrices in the reprsentation is
proportional to the unit matrix.
III.) If Dmm = d for m = 1, 2, , p(< N ), and Dmm 6= Dnn for m, n > p, then D has p-fold degeneracy. Then
corresponding to rst p entries, the o diagonal elements of Ai are zero. Then Ai has a general block-diagonal form,
)
(
X1 0
0 X2
and therefore reducible. X1 , having p diagonal elements forms one-dimensional representations while and X2 represent
irreducible representations of N p dimension.
Schulers second Theorem: If there are two irreducible representations of dimensions d1 and d2 of a group,
then if d1 = d2 , the two representations are either unique or identical. That is the two representations can not be
interconnected by a similarity transformation. If d1 6= d2 , then the two representations are unique.
Proof: Let Ai and Bi form irreducible representations of dimensions d1 and d2 for a group. Let M be a matrix
such that M Ai = Bi M . Then
Ai M = M Bi ,

= Bi M M = M M Bi .

Thus matrix M M commutes with the d2 dimensional representation. Since Bi is irreducible representation by
assumption, according to Schulers rst theorem, M M must be propportional to a unit matrix.
M M = I.
Now if d1 = d2 and 6= 0, M is a unitary matrix and then M Ai M = Bi , the two represntations are equivelant.
If = 0, M is a null matrix and then the two representations are unique (there is no matrix that transforms Ai Bi ).
If d1 6= d2 (let d2 > d1 ), we can create an d2 d2 matrix N = (0, M ). Then N N = M M = I. This implies,
det(N N )=d2 = 0). Thus = 0 and the matrix M is a null matrix. Then the two representations are unique.
Great orthogonality theorem: Let Ai and Bi are two irreducible representations of dimensions d1 and d2 for a
group Gn . Then,
n

(Ai )pq (Bi )p0 q0 = 0

i=1
n

i=1

(Ai )pq (Ai )p0 q0 =

n
pp0 qq0
d

(12)

where sum over i means sum over all elements of the group. Thus sum contains n number of terms which is the order
of the group.

9
Proof: Let
M=

Ai .Y.Bi1

be a d1 d2 matrix. Y is an arbitrary d1 d2 matrix. Then

Al M =
Al Ai .Y.Bi1 =
(Al Ai ).Y.Bi1 Bl1 Bl =
(Al Ai ).Y.(Bl Bi )1 Bl .
i

Now since Al Ai = Aj and Bl Bi = Bj , we can write,

Al M =
Aj .Y.Bj1 Bl ,

= Al M = M Bl .

Then using Schulers theorem, since the two irreducible representations are unique, M is a null matrix. That is any
element Mpq = 0.

Mpq =
(Ai )pp1 Yp1 q1 (Bi )q1 q = 0, = Yp1 q1
(Ai )pp1 (Bi )qq1 = 0.
(13)
i

Since Y is arbitrary, this results in

(Ai )pp1 (Bi ) qq1 = 0

(14)

for all p, q, p1 , q1 .
If d1 = d2 = d and the two representations are equivalent, M = I. Then the o-diagonal elements Mpq are zero,

Mpq =
(Ai )pp1 Yp1 q1 (Ai )q1 q = 0, if p 6= q.
(15)
i

Next we take a trace of M ,

Tr{M } = d =

Tr{Ai .Y.A1
i }=

Tr{Y } = nTr{Y }

i=1

n
n
Tr{Y } =
Ypq pq
d
d pq

Substituting this value of in M = I = i Ai .Y.Ai and taking the element p1 q1 of both sides, we get,

n
Ypq pq p1 q1 =
Ypq
(Ai )p1 p (Ai )q1 q
d pq
pq
i
[
]

=
Ypq
pq p1 q1
(Ai )p1 p (Ai )q1 q = 0
d
pq
i

(16)

(17)

Since Y is arbitrary, we get

(Ai )p1 p (Ai )q1 q =

n
pq p1 q1 .
d

(18)

The two results, Eq. (13) and (18), can be combined together into a single expression into a more general expression.
(k)
If Ai represents dierent irreducible representations for various k values, then we can write
n

(k0 )
)qq1

(k)

(Ai )pp1 (Ai

i=1

n
pq p1 q1 kk0 .
d

(19)

The GOT then establishes a relation between dierent irreducible representations of a group. For a group Gn we
can construct vectors
(k)

(k)

(k)
Vpq
= {(A1 )pq , (A2 )pq , , (A(k)
n )pq }

10
in the space of a group. Then according to the GOT, any two such vectors are orthogonal with respect to any two
conjugate indices. Since group space is n-dimensional, in general, it can have only n-orthogonal independent vectors
which characterize the space. This shows that the maximum number of irreducible representations for a group is
equal to the order of the group.
If the k-th representation is dk -dimensional, it will give d2k orthogonal vectors. Then if there are M representations
of dimensions d1 , d2 , , dM , then total number of orthogonal vectors would be d21 + d22 + + d2M . Form the above
conclusion, this must be less than of equal to the group order, n.
d21 + d22 + + d2M n.

(20)

below we shall see that the equality sign holds.

We can use GOT to further simplify our calculation for an irreducible representation. In Eq. (19), we replace
p1 = p, q1 = q and then we sum over p and q, this gives,
n

(k0 )

(k)

Trace{Ai }Trace{Ai

} = nkk0 .

(21)

i=1
(k)

(k)

This shows that the vectors formed by the traces (character), i = Trace{Ai }, of various representations also
form an orthogonal vectors in the space of the group. Since trace is invariant of the similarity transformation, the
representations for various symmetry operations belonging to the same class have the same characters. This further
simplies the calculation since we only need to consider the traces only for classes (rather than each representation).
(k)
Let be the trace for the -th class which has n number of representations. We can then write the above
equation as sum over classes only,
C

(k )
n (k)
= nkk0

(22)

=1
0

where C is the total number of classes. This can be written as

(k) .
(k ) = kk0 , where
(k) is the normalized vector

(k)
(k)
(k)

(k) = n1/2 { n1 1 , n2 2 , , nC C }
of characters dened in the C-dimensional space which is the number of classes in the group. Since only C orthonormal vectors are possible in a C-dimensional space, the number of irreducible representations for a group with C
classes must be less than or equal to C. In fact it can be shown that there must be eactly C number of irreducible
representations for a group with C classes.
** For an abelian group, since each element is in its own class, the number of irreducible representations are the
same as the order of the group. This combined with the Eq. (20) implies that (this can be shown in a general fashion
by using regular representation of point group)
d21 + d22 + + d2M = n

(23)

that is the sum of the dimensions of all irreducible representations is equal to the order of the group. This is an
important result which let us know if there are any irreducible representation missing or not and combined with the
earlier result that the total number of irr is the same as the class of the group together with the fact that all vectors
in the class space are orthognal, leads to a complete character table for the group.
Now for an abelian group, the number of irreducible representations is the same as the order of the group, M = n.
This result, combined with Eq. (23), leads to the conclusion that all the irr of an abelian group are one dimensional.
[* Find all irr and their dimensionality for C2v and C3v point groups.]
We have seen that the characters (traces) for various representations form a set of orthogonal vectors in the class-space
of a group. These vectors thus form a basis for this space. Then for a given character
of an arbitrary representation
in the th class, we should be able to express it as a linear combination of the basis characters for that class.

ak (k)

=
(24)

This is also clear from that fact that if

is the trace of an arbitray representation for the th class which is reducible,
(k)
then we can make a similarity transformation which will bring the representation into a block-diagonal form. Let

11
be the trace of the kth representation along the diagonal which appears ak times, then since a similarity transformation
does not aects the trace, we can write the above equation. Clearly ak is a positive integer. Thus sum over k means
some over all dierent representations.
(k0 )
We multiply (25) by n
and sum over all . Using Eq. (22), we obtain,
ak =

C
1
(k)
n

.
n =1

(25)

If the trace of the reducible representation is known, then Eq. (25) provides a mechanism to nd out how many times
(k)
the kth representation with trace appears in the reduced form.
Equation (25) is useful in identifying whether a given representation is irreducible or not. This equation can be
used to nd the following expression,
n

a2k =

n |
|2

(26)

=1

If the given representation

is irreducible, then from the GOT, we know that the rhs is equal to n. This implies that

for a given irr, k a2k = 1. Since a0k s are intergers, it is possible only if all ak s are zero except the one which is unity.
If the representation is reducible then there would be more than one non-zero ak s.
Regular representation:
This is a faithful reducible representation for elements of a point group (other than single element groups). It is
constructed from the composition table of a point group. It contains all the irr of the group at least once.
In order to construct this representation, we arrange the composition table of the group such that identity operations
appear along the main diagonal. This table gives us an n n matrix in the space of the group order. Now in order to
obtain the regular representation for an element, we need to replace that element by unity in the matrix with all other
elements replaced by one. By construct, the regular representation for unit operator has trace equal to the order of
the group and traces corresponding to other elements vanish. That is
Reg (I) = n,

Reg (A 6= I) = 0.

We consider the example of C2v point group (H2 O molecule). The group composition table is,

C2v =

I
C2 (yz) (xz)
I
I
C2 (yz) (xz)
C2
I (xz) (yz)
C2
(yz) (yz) (xz) I
C2
(xz) (xz) (yz) C2
I

(27)

This is already in the form where all diagonal elements are I. The corresponding matrix then gives regular representation for dierent elements, such as,

1 0 0 0
0 1 0 0
0 0 1 0
0 0 0 1

0 1 0 0
1 0 0 0
0 0 0 1
0 0 1 0
R(E) =
.
, R(C2 ) =
, R((yz)) =
, R((xz)) =
(28)
0 0 1 0
0 0 0 1
1 0 0 0
0 1 0 0
0 0 0 1
0 0 1 0
0 1 0 0
1 0 0 0
We see that this also gives a valid representation of the group since it preserves the structure of the composition table,
that is, R(C2 )R((yz)) = R((xz)), etc. The characters of the various elements in this representaion are (I) = 4
and others are zero.
Each element is in its own class
in this point group. Thus using Eq. (26), we see that in regular
representation, n |(A )|2 = 16. This gives k a2k = 4. Thus this representation is reducile.
[* Find the regular representation for C3v point group and show that it preserves the composition table for the
group and that the representation is reducible.]

12
In the above example we see that the regular representation is reducible. In fact, this is a general result. Now we
can use the Decomposition theorem to nd out the irr components of this reducible representation. In general, the
character Reg
of the th class in the regular representation is obtained from Eq. (24),

Reg
=
ak (k)

where k runs over all irr. The coecients ak are obtained from (25).
ak =

1
(k)
n Reg
.
n
(k)

If the dimensionality of the kth irr is dk , then for the unit element, = dk and n = 1. Since in regular
representation, all characters
valish except for the unit element, from the above equation, ak = dk . Using above
equation, we then get Reg
= k d2k . Since Reg
= n, we nally get,

d2k = n.
(29)
k

This result, which is called the sum rule, was mentioned earlier in Eq. (23).

13
CHARACTER TABLE

As we have seen so far, characters (traces) of various representations are important to classify operators into
dierent classes and also to determine a particular representation belongs to an irreducible representations or not.
If not, using characters, we can also deteremine which irreducible representations are contained in a given reducible
representation. For this we need to dene character table for a given point group. This table contains all the irr of
the point group and their characters catagorized according to the classes in the group.
The behavior of a general function (usually we are interested in eigenfunctions) under the operation of a group
can be expressed in terms of the behavior of the basis functions that span the space of the group. This is because all
the symmetry operations are some type of coordinate transformations. We can catagorize basis functions in terms of
their behavior under the operation of a group in a table. This table is called the character table.
Character table for C3v point group:

FIG. 1. Showing the coordinate axis for operations in C3v group.Rotation is in the anticlock-wise direction

This point group has six elements, G6 = {I, C3 , C32 , (yz), v , v0 }. Its composition table is given by,

C3v =

I
C3
I
I
C3
C3
C3
C32
I
C32
C32
(yz) (yz) v
v
v
v 0
v 0
v0 (yz)

C32
C32
I
C2
v 0
(yz)
v

(yz) v
v 0
(yz) v
v 0
v0 (yz) v
v
v0 (yz)
I
C3
C32
I
C3
C32
2
I
C3
C3

(30)

From the compositiontable it is clear that operations are their own inverses and C31 = C32 . We then observe that
= C3 , C31 C32 C3 = C32 , C31 (yz)C3 = C32 (yz)C3 = v C3 = v0 , C31 v C3 = C32 v C3 = v0 C3 = (yz),
etc. This shows that all operations belong to a single class while rotation operations form a separate single class.
Thus there are total three classes, {I},{C3 , C32 }, and {(yz), v , v0 }. Then there must be three irr. Let d1 , d2 , and
d3 be their dimensions, then we have,

C31 C3 C3

d21 + d22 + d23 = 6.

This has solutions d1 = d2 = 1, and d3 = 2. Thus there are two 1-D irrs (1 , 2 ) and one 2-D irr (3 ) for C3v group.
We next determine characters of the matrices for group elements under various representations. Let i (A) be the
character of the element A in irreducible representation i . We note that in one-dimensional irr the character of the
unit element is always 1, 1 (I) = 2 (I) = 1 and 3 (I) = 2. We arrange these characters in a table as,
I 2C3
3
1 1 1 (C3 ) 1 ()
2 1 2 (C3 ) 2 ()
3 2 3 (C3 ) 3 ()

(31)

14
In order to determine unknown i in the table, we can use GOT, Eqs. (21) and (22). Applying GOT to these
representations, we obtain,
221 (C3 ) + 321 () = 5, 222 (C3 ) + 322 () = 5, 223 (C3 ) + 323 () = 2.
We also require that these vectors in dierent representations (irr) be orthogonal, that is,
21 (C3 )2 (C3 ) + 31 ()2 () = 1,

21 (C3 )3 (C3 ) + 31 ()3 () = 2, etc.

From the rst equation in teh rst set above, we can choose 1 (C3 ) = 1 () = 1. This gives a unit ir representation.
In the character table for any point group, one of the row for a 1D representation always has all elements unity. A
function with this symmetry possesses the full symmetry of the point group. Once this choice is made, the values for
2 (C3 ) and 2 () have to be chosen such that they satisfy the orthogonality relation (rst equation in the second set),
22 (C3 ) + 32 () = 1. Note that in order to satisfy the second equation in the rst set, 2 can take only values 1.
This condition, together with the orthogonality, leaves only one choice, 2 (C3 ) = 2 () = 1. The nal equations in
the above set then give 3 (C3 ) = 1 and 3 () = 0. Then the character table for the C3v point group is,
I
1 1
2 1
3 2

2C3
1
1
-1

3v
1
-1
0

(32)

[* Construct the character table for a planer molecule AB4 .]

Character table for a cyclic group:
Consider a cyclic group, for example group G4 = {I, C4 , C42 , C43 }. Since C42 = C2 , we have G4 = {I, C4 , C2 , C43 }.
Since each element in a cyclic group is in its own class, there are four classes in cyclic G4 group. Thus according to
GOT, it must have four irreducible representations. If dk is the dimensionality of the kth irr, then d21 +d22 +d23 +d24 = 4.
Then all irr of a cyclic group are of dimension one. Since a group is always its own subgroup, one of the representation
is totally symmetric (all characters unity), we then have,

1
2
3
4

C43
I C4
C42
1
1
1
1
1 2 (C4 ) 2 (C42 ) 2 (C43 )
1 3 (C4 ) 3 (C42 ) 3 (C43 )
1 4 (C4 ) 4 (C42 ) 4 (C43 )

(33)

Since for one dimensional representation, the trace (character) is the same as the matrix, the characters must satisfy
the composition table for the group. Thus
[i (C4 )]4 = 1
This implies that the character for C4 can have four values, 1, 1, i, i.
1
2
3
4

I
1
1
1
1

C43
C4 C42
1
1
1
2
1 2 (C4 ) 2 (C43 )
i 3 (C42 ) 3 (C43 )
i 4 (C42 ) 4 (C43 )

(34)

Further, following the composition table for the group, C4 C43 = I, this implies (C4 )(C43 ) = 1. This determines the
last column of the character table, we get

1
2
3
4

I
1
1
1
1

C4 C42
1
1
1 2 (C42 )
i 3 (C42 )
i 4 (C42 )

C43
1
-1 .
-i
i

(35)

15
Finally, using the orthoganility of vectors in the space of characters, we btain the complete character table,

1
2
3
4

I
1
1
1
1

C4
1
-1
i
-i

C42
1
1
-1
-1

C43
1
-1 .
-i
i

(36)

Note that 3 and 4 represent one dimensional irreducible representations which are complex conjugate of each other.
Such representations correspond to some physical degeneracy in the system, even though they represent separable
one dimensional representations. In this case this degeneracy is due to the choice of x and y axes. Therefore these
complex conjugate representations are written as sum of the two one-dimensional irrs, = 3 + 4 .
I
1 1
2 1
2

C4
1
-1
0

C42
1
1
-2

C43
1
.
-1
0

(37)

Thus represents a two-dimensional representation, which contains two conjugate 1-D irrs.
[* Compute the character table for point group C7 .]
Direct product of groups:
The direct product of two groups Gn = {A1 , A2 , , An } and Gm = {B1 , B2 , , Bm } where all As commute
with all Bs, is dened as, Gn Gm = {A1 B1 , A1 B2 , , A2 B1 , A2 B2 , , An B1 , An B2 , An Bm } and is a group of
order n m.
Consider an equilateral triangle. Its all symmetry operations are given by the symmetry point group C3v . If we
introduce a thickness to this triangle, it gets an additional symmetry (xy) which forms a group C1h = {I, (xy)}.
Note that (xy) commutes with all symmetry operations of C3v . Thus the full symmetry operations of the thick
triangle are given by the direct product of C3v and C1h .
G12 = {I, (xy)} {I, 2C3 , 3v } = {I, 2C3 , 3v , (xy), 2(xy)C3 , 3(xy)v }

FIG. 2. Schematic for a thick equilateral triangle. Its symmetry group is obtained by a direct product of the symmetry group
C3v and C1h point groups.

** Representation of the direct product of groups is obtained from the direct product of the representations of the
individual group elements.

16
** The character table for a direct product group is obtained from the direct product of character tables of the
individual groups.
Group of Hamiltonian
Consider a set of operations {R1 , R2 , , Rn }. If Ri commutes with the Hamiltonian H, and set contains all such
operators, then the set forms a Hamiltonian group.
Ri H = HRi ,

= Rj Ri H = Rj HRi = HRj Ri

(38)

Thus a product Ri Rj also commutes with H and therefore must be in the set. Similarly it can be shown that the
inverse Ri1 also belongs to the set. Thus set contains an identity operation Ri Ri1 = I. Therefore the set of operators
forms a group.
Now let be an eigenstate of H with eigenvalue E, H = E. Let also dene Ri = 0 , then 0 is also an
eigenstate of H with the same energy E. Now if the eigenvalue is nondegenerate, then 0 = eii , where i is an
arbitrary number (phase). This means that and 0 are not distinct eigenfunctions. Then,
Rj Ri = ei(i +j ) = eik = Rk .

(39)

This shows that these phases preserve the composition table of the group of Hamiltonian. Since these phases are just
numbers (1-D matrices), the eigenfunctions of the Hamiltonian corresponding to the nondegenerate eigenvalues form
a 1-D irreducible representation of the group.
Consider application of all operations Ri of the Hamiltonian group on the wavefunction . If it gives l number of
distinct wave functions (dier more than just a phase factor) then the eigenvalue E is said to be l-fold degenerate.
These distinct eigenfunctions can be combined linearly to form a set of l orthonormal degenerate eigenfunctions which
span an l-dimensional Hilbert space. Let i be the ith orthonormal function. Then applying a symmetry operation
on i gives a new function in this space which can be expressed as linear combination of i s.

(Rk )il l
Rk i =
(40)
l

where (Rk )il = il (Rk ) is the matrix representation of the operator Rk in the basis of degenerate functions, i . This
representation is an l dimensional irreducible representation of the group. This can be shown as follows. If the representation in terms of degenerate eigenfunctions is reducible, then we should be able to nd a similarity transformation
to reduce it to a (block) diagonal form. If this is possible, let us say after the reduction, we nd that the rst block
is 2 2. Then application of any operation on 1 (2 ) will couple it to only 2 (1 ). There is no operation that will
couple it to other eigenfunctions. Then 1 and 2 are said to span a separate 2-D space. That means that 1 and 2
live in a space which is orthogonal (has no intersection with) to the l 2 dimensional space spanned by the rest of l 2
wavefunctions. Then thy must correspond to a dierent eigenvalue. This is against the initial assumtion. Thus the
representation in terms of degenerate eigenfunctions i must be an irreducible representation. The degree of degeneracy of molecular energy level is equal to the dimension of the irreducible representation.
O-H vibrations in H2 O:
Let us consider stretching of O H bonds in the water molecule. They are seem identical, thus neively it seems
that they both vibrate with the same vibrational frequency. Thus in IR spectroscopy, we should expect to see a single
peek. Lets apply group theory methods to study this.
We consider O H1 and O H2 bonds as basis for expressing the symmetry operations for the water molecule
which has C2v = {I, C2 , v , h } point group. Since each element in this point group has its own class, we have four
irr for this group. The character table for this group is,
1
2
3
4

I
1
1
1
1

C2
1
-1
1
-1

v
1
1
-1
-1

h
1
-1
-1
1

(41)

We apply group operations to the vector formed by the basis functions (2 O H bonds). I and h do not do any
changes, C2 and v interchange the two bonds.
(
) (
)
(
) (
)
O H1
O H1
O H1
O H2
I
=
, C2
=
.
O H2
O H2
O H2
O H1

17

FIG. 3. Schematic for a H2 O molecule.

Therefore the representation of these operations in the basis of the two bonds is,
)
(
)
(
1 0
0 1
, C2 = v =
.
I = h =
0 1
1 0

(42)

Then the traces (characters) are, (I) = (h ) = 2 and (C2 ) = (v ) = 0. Is this representation irreducible? We
can use previous discussion (Eqs. (25) and (26)) to check the irreducibility of this representation.

n | |2 = 4 + 0 + 0 + 4 = 8, n
a2k = 4
a2k , Since n
a2k =
n | |2 , =
a2k = 4.

This shows that this representation is reducible. We next check if this representtion contains any of those listed in the
table. For this we apply the Decomposition theorem, Eq. (25), which gives how many times (ak ) the kth irr appears.
Thus,
a1 =

1
1
1
1
1
= (2+0+0+2) = 1, a2 = (2+0+02) = 0, a3 = (2+0+02) = 0, a4 = (2+0+0+2) = 1.
n
irr

n
4
4
4
4

We thus see that the irr ( = 2, 0, 0, 2) formed by the basis of O H bonds contains irr 1 and 4 , = 1 + 4 . Since
both 1 and 2 are nondegenerate 1D representations, is also nondegenerate. Thus two O H vibration bonds can
not be degenerate.
[* Show that functions (x2 y 2 , xy) form a 2-D irreducible representation of C3v group.]

18
SYMMETRY ADAPTED LINEAR COMBINATIONS

Direct product of groups and their representations are used to determine various selection rules based on integrals.
The symmetry arguments can only tell whether a particular transition between two states is allowed or not allowed,
it does not give an absolute value of the transition, that is the strength of the transition. Let us consider a matrix
element,

Mij = hi|V |ji = dxi (x)V j (x).

(43)
Here V is a parturbation which causes the transition between the two states and the total Hamiltonian is H = H0 +V .
The symmetry operations of H0 are known. Let us assume that the function i (j ) transforms according to an
irreducible representation i (j ). If V transforms as irreducible representation , then the product i (x)V transforms
as the direct product i . Since vectors of dierent irreducible representtions are orthogonal, the matrix element
is zero unless the direct product i is the same as j or contains this representation.
Thus in order to determine selection rules we need to know the symmetry of various functions and their products.
It is therefore useful to express any arbitrary function in terms of with known symmetries. These known functions
are called symmetry adapted functions (SAF). If an arbitrary function contains more tahn one SAF, we cal it linear
combination of SAF. In order to nd out these SAFs in an arbitrary function, we can make use of a projection operator
that projects out these functions from the arbitrary function. This is similar to the projection operator dened in a
Hilbert space of a system using eigenfunctions which projects out dierent components from an arbitrary vector belonging to the symmetries of the eigenfunctions. In group theory, this projection operator is dened in the group space
spanned by the symmmetry operations of the system. Since each distinct symmetry is characterized by a character,
the projection operator projects out various functions belonging to dierent characters (symmetry) of a representation.
Projection Operator:
(k)

Let i is the ith function of the basis set that gives kth irreducible representation of dimension dk of a group
Gn = {A1 , A2 , , An }. Then,
(k)

A i

dk

(k)

(A(k)
)ij j

(44)

j=1
(k)

Multiplying this equation by (A

)mm0 both sides and summing over , we get,

(A(k)
)mm0 A i

(k)

dk

(k)
)mm0 (A(k)
(A
)ij j

(k)

j=1

dk

n
(k)
mi m0 j j
d
k
j=1

n
(k)
mi m0
dk

(45)

where in the second line we have used the GOT, Eq. (19). Puting m0 = m and then summing over m, we obtain,
dk (k)
(k)
(k)
A i = i ,
n

(k)

= P (k) i

(k)

= i

(46)

where
P (k) =

dk (k)
A
n

(47)
(k)

is a projection operator and from the above equation (46) we conclude that if i forms a basis for the kth irreducible
representation, then it is an eigenfunction of the projection operator with eigenvalue unity. Note that if is any
function which is a linear combination of basis functions for various irreducible representations, then P (k) projects
(k0 )
out only those components from which belong to the kth irreducible representation. This is becasue P (k) i = 0
due to GOT. Thus projection operator allows us to check whether a given function forms the basis of a particulrar

19
irr or not and if there is any component in an arbitrary function that belongs to a particular irr.
In the H2 O example above, we found that if we choose orbitals of the hydrogen atoms as the basis, then we
get a reducible representation which contains two irr 1 and 4 . We now ask the question, what is the correct
linear combination of the basis functions to form molecular obtials which is consistent with the symmetry of the H2 O
molecule? Since contains two irr, the resulting molecular orbitals must satisfy symmetry requrements of 1 and 4 .
Thus we must have two indepndent molecular orbitals corresponding to two irrs. We rst construct molecular orbital
for irr 1 by applying the projection operator P 1 to basis function (O H1).
n (k)
P 1 (O H1) =
A (O H1)
dk
1
[I(O H1) + C2 (O H1) + v (O H1) + h (O H1)]
4
1
1
= [(O H1) + (O H2) + (O H2) + (O H1)] = [(O H1) + (O H2)].
4
2
=

Thus one molecular orbital is given by the sum of two basis functions devided by 2. We next apply P 4 to the basis
function to get the other function consistent with the symmetry of 4 .
1
[I(O H1) C2 (O H1) v (O H1) + h (O H1)]
4
1
1
= [(O H1) (O H2) (O H2) + (O H1)] = [(O H1) (O H2)].
4
2

P 4 (O H1) =

This gives the other molecular function. These are called bonding and anti-bonding orbitals, respectively. These two
molecular oritals are orthogonal and correspond to the two normal modes of vibrations discussed earlier.
SALC for C2 H4 :
We consider four sigma hydrogen orbitals s1 , s2 , s3 and s4 as basis for constructing the symmetry adapted molecular
orbitals for C2 H6 . This molecule belongs to the point group D2h , G8 = {I, C2 (z), C2 (y), C2 (x), i, (xy), (xz), (yz)}.
We next construct the character table for the point group. From the composition table of this group, we nd that

FIG. 4. Schematic for a C2 H4 molecule. s1 , s2 , s3 and s4 are the hydrogen atomic orbitals participating in the molecular
bonding.

there are total 8 classes. Therfore, there are 8 irr. Since the number of irr is the same as the order of the group, all
irr are one dimensional.
1
2
3
4
5
6
7
8

I C2 (z) C2 (y) C2 (x)

1 1
1
1
1 1
-1
-1
1 -1
-1
1
1 1
1
1
1 -1
1
-1
1 -1
-1
1
1 1
-1
-1
1 -1
1
-1
4 0
0
0

i (xy) (xz) (yz)

1
1
1
1
-1 -1
1
1
1 -1
-1
1
-1 -1
-1
-1
1 -1
1
-1
-1 1
1
-1
1
1
-1
-1
-1 1
-1
1
0
4
0
0

(48)

20
We next apply dierent operations of the group to the basis functions and note how they transform. For example
C2 (z) transforms (s1 , s2 , s3 , s4 ) (s3 , s4 , s1 , s2 ). Thus, in this basis, C2 (z) is represented by a 4 4 matrix with zero
trace. Only operations with nonzero race are those which leave at least one basis function unchanged. These are I
and (xy). Since they leave all basis functions unaected, the trace of the corresponding matrix representation is 4.
Thus in this basis, we have a representation shown in the last row of the character table. We can check whether
this representation is reducible or not.

n | |2 = 16 + 16 = 32, and n = 8, =
a2k = 4.
(49)

2
k ak

Since
> 1, this representation is reducible. We next use the decomposition theorem to nd out how many irr
are present in this representation. For the representation 1 , we have
a1 =

1
1
1

= [4 + 4] = 1.

n
8

Thus representaiton 1 appears once in this representation. Similarly,

a2 =

1
[4 4] = 0 = a3 = a4 = a5 , a6 = a7 = a8 = 1.
8

Thus representations 1 , 6 ,7 , and 8 appear once in representation formed by the basis set (s1 , s2 , s3 , s4 ). We
next need to combine our basis functions such that the combinations conform with at least one of these irr. For this
we make use of the projection operator. We apply P 1 to s1 ,
P 1 s1 =
=

dk 1
A s1
n
1
1
[s1 + s3 + s2 + s4 + s3 + s1 + s4 + s2 ] = [s1 + s2 + s3 + s4 ].
8
4

This gives one molecular orbital which is consistent with symmetry of representation 1 . Similarly, we get
1
[s1 s3 s2 + s4 s3 + s1 + s4 s2 ] =
8
1
P 7 s1 = [s1 + s3 s2 s4 + s3 + s1 s4 s2 ] =
8
1
8
P s1 = [s1 s3 + s2 s4 s3 + s1 s4 + s2 ] =
8

P 6 s1 =

1
[s1 s2 s3 + s4 ]
4
1
[s1 s2 + s3 s4 ]
4
1
[s1 + s2 s3 s4 ].
4
(50)

These give the other three symmetry adapted molecular orbitals for C2 H4 molecule.