Application of group theory to IR and Raman spectroscopy

 Molecule at ordinary temperature exhibit translational, rotational and vibrational motion.

Molecules having N atoms have 3N degrees of

freedoms (as 3N position coordinates changes
in time, description need specification of them)

 Translational motion can be specified by specifying thee position coordinate of the

molecules' center of the mass. Thus three degrees of freedom belong to the translational
motion.

 Similarly, 3 degrees of freedom go to the rotational motion for non-linear molecules. However, it is two for a
linear molecules.

 To this end:
There are (3N-6) degrees of freedom for non-linear molecules ; for linear molecules number of vibrational
degrees of freedom is 3N-5
 Molecules vibrate in a complicated way

Lets say the molecule comprised of N atoms whose positions in

space specified by the coordinates

 Potential energy associated with this type of motion is a

V ({xi })
complicated functions of the position of all atoms
 In the equilibrium (state of the lowest energy), the values of these coordinates may be denoted by ( x1 , x 2 ,....., x 3 N )
Expanding potential energy in Taylor series around the equilibrium position
 V  1   2V 
V ({xi })  V ({xi })     ( xi  xi )    ( xi  xi )( x j  x j ) .....
i  xi  ( xi ) ( xi ) 2 i , j  xix j 
 xi  xi ; x j  x j

 V  1   2V 
V ({ x i })  V ({ x i })     ( xi  xi )     ( x i  x i )( x j  x j )  .....
i  xi 2 
i , j  xix j

 ( xi )  ( xi )  xi  xi ; x j  x j

Constant zero

1   2V 
V ({ x i })  V 0  0 
2
 

i , j  xix j


( x i  x i )( x j  x j )  Ignoring higher order terms as
 ( xi )  ( xi ) displacement from the equilibrium
position is small
2nd order terms  harmonic
component of the atomic vibrations

1   2V  1 It contains cross-terms
V ({ x i })  V 0 
2
 

i , j  xix j


( x i  x i )( x j  x j )  V 0 
2
 f ij q i q j
 difficult to handle
 xi  xi ; x j  x j i, j

  2V 
where, f ij    ; qi  m i ( xi  xi )

i , j  q iq j

 qi  0;q j  0
 1 1
H 
2
 q i2 
2

i, j
f ij q i q j

H 3N
p i   ; qi    f ij q j ; i  1, 3 N
q i j 1
It contains 3N variables, difficult to solve. We
need to play some trick so that all equations
H
q i  ; qi   f i1 q1  f i 2 q 2  f i 3 q 3  ...  f i 3 N q 3 N ; become of single variables
p i

These set of 3N coupled second order Where the matrix f is a real symmetric matrix, with can be
differential equation can be expressed as diagonalized using suitable unitary transformation

 q1   f 11 f 12 . . f 13 N   q1  Where, L is a diagonal matrix

 q   f f 22 . . f 2 3 N  q  U  1 fU  Λ ;  1 0 . . 0 
 2   21  2  0
 .   . . . . .   . 0 f  UΛU 1
 2 . . 0 
      Λ . . . . . ;
 .   . . . . .   .   
 q3 N   f 3 N 1 f3N 2 . . f 3 N 3 N   q 3 N   . . . . . 
 0 0 . .  3 N 
1
q
  fq  0 ; q
  U Λ U q0
1, 2, … 3N  Eigenvalues of f;
1 1
U q
  Λ U q0 the columns of U are the corresponding eigenvectors
 1, 2, … 3N  Eigenvalues of f;
L is a diagonal matrix
the columns of U are the corresponding eigenvectors
U 1
q
  Λ U 1
q0  1 0 . . 0   a11 a12 . . a13 N 
0  a
 2 . . 0 
 21 a 22 . . a 2 3 N 
  ΛQ  0
Q Λ . . . . . ; U   . . . . .  ;
   
 . . . . . 
 . . . . . 
Where, QU q 1
 0 0 . .  3 N   a 3 N 1 a3 N 2 . . a 3 N 3 N 

1
Q    1 0 . . 0   Q1   Q1   a11 a12 . . a13 N   q1 
1
   0 Q  a a 2 3 N  q 
 Q2   2 . . 0  Q 
 2   2   21 a 22 . .  2 
 .   . . . . .   . 0  .  . . . . .   . 
           
 .   . . . . .   .   .   . . . . .   . 
Q   0 0 . .  3 N   Q 3 N   Q 3 N   a 3 N 1 a3 N 2 . . a 3 N 3 N   q 3 N 
 3N 

   Q  0
Q Where,
1 1 1

   Q  0 Q 1  a11 q1  a 21 q 2  a 31 q 3  ...  a 3 N 1 q 3 N We now introduce a new set of coordinates

Q 2 2 2
Q i  a1i q1  a 2 i q 2  a 3 i q 3  ...  a 3 N i q 3 N {Q i } that allow to express 3N coupled
   Q  0
Q i i i equations into three 3N one variable equations
 Q 1  a11 q1  a 21 q 2  a 31 q 3  ...  a 3 N 1 q 3 N 1
 Q1   a11 a12 . . a13 N   q1 
Q 2  a11 q1  a 21 q 2  a 31 q 3  ...  a 3 N 1 q 3 N Q  a
 2   21 a 22 . . a 2 3 N  q 
 2 
 .  . . . . .   . 
.      
.  .   . . . . .   . 
Q i  a1i q1  a 2 i q 2  a 3 i q 3  ...  a 3 N i q 3 N  Q 3 N   a 3 N 1 a3 N 2 . . a 3 N 3 N   q 3 N 

Transfer matrix
Rq 1  c11 q1  c 21 q 2  c 31 q 3  ...  c 3 N 1 q 3 N
 a11 a12 . . a13 N 
Rq 2  c11 q1  c 21 q 2  c 31 q 3  ...  c 3 N 1 q 3 N a
 21 a 22 . . a 2 3 N 
. U T   . . . . . 
 
.  . . . . . 
Rq i  c1i q1  c 2 i q 2  c 3 i q 3  ...  c 3 N i q 3 N  a 3 N 1 a3 N 2 . . a 3 N 3 N 
 Hamiltonian
1 1
H   q i2   f ij q i q j
2 2 i, j

We now introduce a new set of coordinates {Qi} that allow to express the Hamiltonian
without any the cross terms, i.e.

1 1 Qi  Normal coordinate and harmonic motion along such each coordinate is

H 
2
 Q i2  2 Q
i
i i
2
called normal mode of vibration.
 Normal mode of vibration refer to movement of a group of atoms.
H  H i  There are six (for non-linear molecules) or five (for linear molecules) normal
coordinate for which  = 0. They correspond to translational and rotational
 Sum of single mode normal coordinates
Hamiltonain, with

1 2 1
Hi  Q i   i Q i2 Total vibrational wave function
2 2
Wave function for the k-th normal    v(11) v(22 ) .... v(kk )
mode of vibration

 (k )
v
k
 N Hv
v     k Q k2 
 k Q k exp  
2

 
 Normal modes as basis of irreducible representation
1 2  1 Ground states:
H 
2
 i 2
Q Q i i
2

i Lowest vibrational state of the molecule means all the

 As the Hamiltonian remains invariant, under action normal vibrational modes are in the ground state, v = 0
of any symmetry operation of the molecule. Under
action of symmetry operation, the normal modes Total vibrational wave function in the ground state.
should change as :  0   0(1) 0( 2 ) .... 0( k ) ...
When normal modes
Thus, acts a base of one   1Q12    2 Q 22    k Q k2 
are non-degenerate
dimensional representation  N 1 exp    . N 2 exp    ... N k exp    ...
 2   2   2 
Rˆ Q k   Q k
 1  k Q k2  Remain invariant under symmetry
 N exp     operation . Thus, 0 belong to the
If the k-th mode is d-fold degenerate : {Q
(1 )
,Q (2)
,.. Q (d )
}  2 k 2 
k k k
totally symmetric representation
d
Rˆ Q (i )
k  a li Q k( l )
1
 
l 1
E0  k
 Thus, it can be shown that this set of degenerate 2 k

modes can act as base of a d-dimensional irreducible

representation of the point group of the molecule.
 Fundamental levels:

1( k )   0(1) 0( 2 ) .... 1( k ) ... One normal mode is in the 1 excited

st

state and rest are in the ground state Overtone levels :

1st overtone
As 1st exited state of k-th mode is as, 2nd overtone
  k Q k2  So on
 1
(k )
 C Q k exp   
 2 
Combination levels
Thus, one can expressed wavefunction of
fundamental levels as

1( k )  Constat  Q k  0

As 0 is totally symmetric, symmetry of the fundamental level , 1 (k) ,

is the same as the k-th normal mode coordinate Qk
Energy of the fundamental levels

E 1( k )  E 0    k
 Group theoretical condition for vanishing an integral   *f Oˆ  i

Suppose:
 f * belong to some irreducible representation Df Then this integral will non-zero only if direct
product of these irreducible representation
 O belong to some irreducible representation Dl contains a totally symmetric representation.

 j * belong to some irreducible representation Di D f

 D l  D i  D 1  D 2 ...

Important theorems:
Direct product of an irreducible representation with itself contains totally symmetric representation once. However, in direct
product of two different irreduciable representations does not contain totally symmetric representation never occurs.
Use the standard reduction formula to get number of times totally
Di  D j
  i j symmetric representation appear in the direct product.
1 1 1
 i j
(R)   (R) (R)
i j 1 
g
 [  1 ( R )]*[  i i ( R )]  g
 1*[  i ( R )] * [  i ( R )] 
R g
g 1
R

1 1
1 
g
 [  ( R )] [ 
1 * i j
( R )] 
g
1 [
R
* i
( R )] * [  j ( R )]  0
R
 The condition of a molecule to be IR active and selection rule
Due to interaction with light, there might be The interaction energy,
transition between two vibrational levels     dipole moment
U    .E
E  electric field due to light
Condition for the transition:
Ei Ef v  is a function of displacement from the
equilibrium bond length. Thus we can write,
 
 f |E . |  i  0 d 1 d 2
  ( q )   ( 0)  q q2  . . . . .
 dq 2! dq 2
 E .  f | |  i  0 q 0 q 0

  f | |  i  0  Taking up to leading order transition

 d 
 ( q )   (0)    q
This integral known as transition dipole  dq  q  0
moment . If this integral is large,
transition intensity will be large, if zero Permanent dipole Rate of change of dipole moment
moment due to displacement from the
there will be no transition at al.
equilibrium position
 Condition to be IR active

In case of IR spectroscopy, transition is electric dipole induced.

 ˆ 
*
i f  0 Here,  transform as x, y, z

Condition to a fundamental band to be appeared:

  0* ˆ  1( i )  0 Thus, integral will be non-zero if  and Qi belong to the same

irreducible representation.

Thus, the condition for i-th fundamental band appears is as

  0* ˆ Q i  0  0 follows:
The irreducible representation where the normal mode Qi is a

D1  D  D i  .. basis , should contain any one or two or all of x, y, z as a basis.
 Condition to be Raman active
 In case of Raman , the dipole is induced dipole
  i* ˆ  f  0
Induced dipole is related to the
molecular polarizability as,
 ind   E
Condition to a fundamental band to be appeared:
Thus, integral will be non-zero if  and Qi belong to the same
  i  0
*
f irreducible representation.

Note that Polarizability tensor  transform as quadratic

  Qi0  0
*
0 functions: x2, y2, z2, xy, xz, yz

Thus, the condition for i-th fundamental band appears is as

D 1  D   D i  .. follows:
Check The irreducible representation where the normal mode Qi is a
basis , should contain any one or their linear combination all of
the quadratic functions x2, y2, z2, xy, xz, yz as a basis.
 Mutual exclusion rule
Conditions to be IR active: Normal mode should belong to an irreducible
representation where linear functions x, y, z can act as a basis.

Conditions to be Raman active: Normal mode should belong to an irreducible

representation where quadratic functions x2, y2, z2, xy, xz, yz can act as a basis.

In center symmetric molecule both linear and quadratic function simultaneously cannot be
basis of an irreducible representations. Thus, if a mode is Raman active cannot be IR active
and vice verse
 Determination symmetry of normal models
Supposed we construct a representation using 3N Representation using normal coordinates {Qi} as a bases
position coordinates {qi} of N atoms as bases.
a c d 0 0 0 0 0 .. .. .. 0
1 c d 2 0 4 a 0 .. .. .. 1  b
b d d 0 0 0 0 0 .. .. .. 0 
 0 d 0 0 0 0 0 .. .. .. 0  This similarity transform 
0 3 0 0 0 0 0 0 .. .. .. 0
0 0 0 w 0 0 0 0 .. .. .. 0  convert matrix in a block  

0 0 0 0 0 q 0 0 .. .. .. 0 

diagonal form 0 0 0 2 3 0 0 0 .. .. .. 0
0 0 0 0 0 0 a 0 .. .. .. 0 
0 0 0 1 1 0 0 0 .. .. .. 0
   
3 0 3 0 0 0 .. .. .. 0  0 0 0 0 0 2 3 0 .. .. .. 0
D Q (R)  
k r
D x (R)   .
0 5 v 2 1 3 0 v .. .. .. 0  0 0 0 0 0 5 1 0 .. .. .. 0
   
0 0 0 d 0 0 0 0 .. .. .. d  0 0 0 0 0 0 0 s .. .. .. 0
0 0  0

a 0 0 0 0 d 0 .. .. ..
 0 0 0 0 0 0 p .. .. .. 0
 ..
 
.. .. .. .. .. .. .. .. .. .. .. 
   .. .. .. .. .. .. .. .. .. .. .. 0
 .. .. .. .. .. .. .. .. .. .. .. ..   
 a c b 0 0 0 b 0 .. .. .. a   .. .. .. .. .. .. .. .. .. .. .. 0
 0 0 0 0 0 0 0 0 .. .. .. a 
1
We know that normal coordinates Qi are QT q
obtained with suitable linear combination {qi} Transfer matrix The representative matrix for the
Q 1  a11 q1  a 21 q 2  a 31 q 3  ...  a 3 N 1 q 3 N  a11 a12 . . a13 N  symmetry operation R in {xi} and {Qi}
a a 22 . . a 2 3 N  basis are related by a similarity
Q 2  a11 q1  a 21 q 2  a 31 q 3  ...  a 3 N 1 q 3 N  21
T  . . . . .  transform:
. ..  
Q i  a1i q1  a 2 i q 2  a 3 i q 3  ...  a 3 N i q 3 N  . . . . . 
D Q ( R )  T  1 D x ( R )T
 a 3 N 1 a3 N 2 . . a 3 N 3 N 
 Determination symmetry of normal models
Supposed we construct a representation using 3N Representation using normal coordinates {Qi} as a bases
position coordinates {xi} of N atoms as bases. D1 a c d 0 0 0 0 0 .. .. .. 0
1 c d 2 0 4 a 0 .. .. .. 1  b
b d d 0 0 0 0 0 .. .. .. 0 
 0 d 0 0 0 0 0 .. .. .. 0  This similarity transform 
D2
0 3 0 0 0 0 0 0 .. .. .. 0
0 0 0 w 0 0 0 0 .. .. .. 0  convert matrix in a block  

0 0 0 0 0 q 0 0 .. .. ..

0  diagonal form 0 0 0 2 3 0 0 0 .. .. .. 0
0 0 0 0 0 0 a 0 .. .. .. 0 
0 0 0 1 1 0 D3 0 0 .. .. .. 0
   
3 0 3 0 0 0 .. .. .. 0  0 0 0 0 0 2 3 0 .. .. .. 0
 
k r
D x (R)   . D Q (R)
0 0 0 0 0 5 1 0 0

0 5 v 2 1 3 0 v .. .. .. 0
  D..4 .. ..

0 0 0 d 0 0 0 0 .. .. .. d  0 0 0 0 0 0 0 s .. .. .. 0
0 0  Note that 0

a 0 0 0 0 d 0 .. .. ..
 0 0 0 0 0 0 p .. .. D..5 0
 ..
 
.. .. .. .. .. .. .. .. .. .. ..  Tr { D x ( R ) }  Tr { D Q ( R ) }
   .. .. .. .. .. .. .. .. .. .. .. 0
 .. .. .. .. .. .. .. .. .. .. .. ..   
 a c b 0 0 0 b 0 .. .. .. a   .. .. .. .. .. .. .. .. .. .. .. 0
D6
 0 0 0 0 0 0 0 0 .. .. .. a 

Such portioning means  under all symmetry operations of the Basis function are portioned as:
group, functions of any subset remain linear combination of the {Q1, Q2, Q3}  Form irreducible representation D1
same subset. Do not mixed with functions of other subset. {Q4, Q5}  Form irreducible representation D2
RQ 1  a 1 Q 1  a 2 Q 2  a 3 Q 1 ; RQ 5  b1 Q 4  b 2 Q 5 So on ..
 Determination symmetry of normal modes
Supposed we construct a representation using 3N Representation using normal coordinates {Qi} as a bases
position coordinates {xi} of N atoms as bases. D1 a c d 0 0 0 0 0 .. .. .. 0
1 c d 2 0 4 a 0 .. .. .. 1  b
b d d 0 0 0 0 0 .. .. .. 0 
 0 d 0 0 0 0 0 .. .. .. 0  This similarity transform 
D2
0 3 0 0 0 0 0 0 .. .. .. 0
0 0 0 w 0 0 0 0 .. .. .. 0  convert matrix in a block  

0 0 0 0 0 q 0 0 .. .. ..

0  diagonal form 0 0 0 2 3 0 0 0 .. .. .. 0
0 0 0 0 0 0 a 0 .. .. .. 0 
0 0 0 1 1 0 D3 0 0 .. .. .. 0
   
3 0 3 0 0 0 .. .. .. 0  0 0 0 0 0 2 3 0 .. .. .. 0
 
k r
D x (R)   . D Q (R)
0 0 0 0 0 5 1 0 0

0 5 v 2 1 3 0 v .. .. .. 0
  D..4 .. ..

0 0 0 d 0 0 0 0 .. .. .. d  0 0 0 0 0 0 0 s .. .. .. 0
0 0  Note that 0

a 0 0 0 0 d 0 .. .. ..
 0 0 0 0 0 0 p .. .. D..5 0
 ..
 
.. .. .. .. .. .. .. .. .. .. ..  Tr { D x ( R ) }  Tr { D Q ( R ) }
   .. .. .. .. .. .. .. .. .. .. .. 0
 .. .. .. .. .. .. .. .. .. .. .. ..   
 a c b 0 0 0 b 0 .. .. .. a   .. .. .. .. .. .. .. .. .. .. .. 0
D6
 0 0 0 0 0 0 0 0 .. .. .. a 
To determination symmetry of normal modes
 Eliminate irreducible representations associated
 Get character of representative matrix (in {xi} or {Qi} basis) for
translational and rotational degrees of freedom to get
the symmetry operations of the point group.
irreducible representation for normal vibrational
 Using standard reduction formula number of times irreducible
modes only .
representation appear in the reducible representation.
 Identify irreducible representations associated translational
The final step is to identify irreducible
and rotational degrees of freedom.
representation for individual modes.
To determination symmetry of normal modes
 Get character of representative matrix (in {xi} or {Qi} basis) for Eliminate irreducible representations
the symmetry operations of the point group. associated translational and rotational degrees
 Using standard reduction formula number of times irreducible of freedom to get irreducible representation for
representation appear in the reducible representation normal vibrational modes only
 Identify irreducible representations associated translational
and rotational degrees of freedom. The final step is to identify irreducible
representation for individual modes.
We start with of water molecule
Z Based on the following notes one easily get characters for the representative
(x1, x2 , x3) matrices.
Y O
If a basis remains unchanged under symmetry operation contribute one to
X diagonal element of representative matrix.
H H
If basis change the sign without being shifted or changing magnitude, it contribute
(x4, x5, x6) (x7, x8, x9) -1 to the diagonal elements of representative matrix.
If we consider representative If basis function changes to a new function or basis vector is shifted , it contribute
matrix using Cartesian coordinates zero to the diagonal elements of representative matrix.
as a basis. We will get 9 x 9
representative matrices E C2(Z) sv (XZ) s v(YZ)
R 9 -1 1 3
 Z C2v Character table Basis Functions
(x1, x2 , x3) E C2(Z) sv (XZ) s v(YZ) Linear Quadratic
O
Y
A1 1 1 1 1 z, pz z2, x2, y2, dx2-y2
X A2 1 -1 -1
1 Rz xy, dxy
H H
B1 1 -1 1 -1 x, px, Ry xz, dxz
(x4, x5, x6) (x7, x8, x9)
B2 1 -1 -1 1 y, py, Rx yz, dyz
1
g R

i [  i ( R )]* [  r ( R )] r 9 -1 1 3
Use standard reduction formula to express reducible total   r  3 A1  A2  2 B1  3 B 2  tr  rot  vib
representation as a direct sum of irreducible representation.
This includes all motions: Translational +Rotational + Vibrational
1
 A1  (1 * 9  1 * (  1)  1 * (1)  1 * (3))  12 / 4  3 tr  adding irreducible
4 representation whose basis are tr  A1  B1  B 2
1 x,y,z . Thus, from character table.
 A2  (1 * 9  1 * (  1)  1 * (1)  1 * (3))  4 / 4  1
4
rot  adding irreducible
1 representation whose basis are rot  A2  B1  B 2
 B1  (1 * 9  1 * (  1)  1 * (1)  1 * (3))  8 / 4  2
4 Rx,Ry,Rz . Thus, from character table.

1 vib  Can be obtained by vib  total  tr  rot

B  (1 * 9  1 * (  1)  1 * (1)  1 * (3))  12 / 4  3
2
4 eliminating and from tot
 2 A1  B 2
 C2v Character table Basis Functions
E C2(Z) sv (XZ) s v(YZ) Linear Quadratic
Z
(x1, x2 , x3) A1 1 1 1 1 z, pz z2, x2, y2, dx2-y2
O
Y A2 1 1 -1 -1 Rz xy, dxy
X B1 1 -1 1 -1 x, px, Ry xz, dxz
H H B2 1 -1 -1 1 y, py, Rx yz, dyz
(x4, x5, x6) (x7, x8, x9) R 9 -1 1 3

vib  2 A1  B 2  This means two normal modes

are A1 types and one is B2 type
Check whether these modes are Raman and IR active or not

 A1 modes contain z as a basis, thus become IR active due to z-component of dipole moment
 B2 mode contains y as a basis, thus become IR active due to y-component of dipole moment

 A1 modes contain quadratic functions x2 , y2, z2 as basis, thus become Raman active.

 B2 mode contains quadratic functions yz as a basis, thus become Raman active.

 Character table Basis Functions
E 2C3 3C’2 sh 2S3 3s v Linear Quadratic
Consider the following toltal 12 0 -2 4 -2 2
example
 cos  sin  0  cos  sin  0
Note:    
D(Cn )    sin  cos  0 D( S n )    sin  cos  0
 0  0  1
 0 1   0

Tr {D(Cn )}  2 cos   1 Tr {D(Cn )}  2 cos   1

 Consider the
following example

Use standard reduction formula to express reducible Character table

representation as a direct sum of irreducible representation. E 2C3 3C’2 sh 2S3 3s v
toltal 12 0 -2 4 -2 2
total  A1  3 E   2 A2  E   tr  rot  vib

tr  adding irreducible representation whose basis are x,y,z. tr  E   Á 1
Thus, from character table.

rot  adding irreducible representation whose basis are Rx,Ry,Rz .   A  E 

rot 2
Thus, from character table.
vib  Can be obtained by eliminating and from tot vib  total  tr  rot  A1  2 E   A2
 vib  A1  2 E   A2  This means two normal modes are E’’ Assignment:
types , one is B’1 type and one is A’’2 type
Find irreducible representations for the
Check whether these modes are Raman and IR active or not following molecules. Check their Raman
 A’1 mode does not contain x/y/z as a basis, thus become IR inactive. and IR activity,
 E’1 modes contain (x,y) as a basis, thus become IR active.
NH3 & XeF4
 A’’1 mode contains z as a basis, thus become IR active.

-- -- on the same line of reasoning we can check whether these

modes are Raman active or not.
 Projection operator Lets define an operator to project out desire parts of the
vector. We start with an operator which project out x-
Consider a vector in 3 dimensional physical space component of vector

v  a iˆ  bˆj  c kˆ  ˆˆ ˆ ˆ
 
pˆ i  i i ; p i v  i i a i  b j  c kˆ  a iˆiˆ.iˆ  b iˆiˆ. ˆj  c iˆiˆ.kˆ
ˆ ˆ ˆ

Projection of the vector v along X axis will gives a iˆ  a iˆ  b iˆ.0  c iˆ.0  a iˆ
Similarly if we define: pˆ j  ˆjˆj ; pˆ k  kˆkˆ

Projection of the vector v on XY axis will give is a iˆ  bˆj 
 
pˆ v  ˆjˆj a iˆ  bˆj  c kˆ  aˆjˆj.iˆ  bˆjˆj. ˆj  cˆjˆj.kˆ  bˆj
j

ˆp v  kˆkˆ a iˆ  bˆj  c kˆ   c kˆ; ( pˆ  pˆ ) v  a iˆ  bˆj

 
More general definition: k i j
 Lets {i} form a complete and ortho-normal basis set.  
( pˆ i  pˆ j  pˆ k ) v  a iˆ  bˆj  c kˆ  v
Thus, any vector in the space can be written
n Thus, ( pˆ i  pˆ j  pˆ k )  Iˆ  acts as an identity operator
  c1  1  c 2  2  ....  c i  i  ...  c n  n   c i  i
i 1

Here projection operator is define as, pˆ i   i  i

pˆ i    i  i c1  1  c 2  2  ....  ci  i  ...  c n  n  c i  i  Project out i-th component of the vector

n n
 Some important properties of projection operators  pˆ i   ;  pˆ i  Iˆ  identity
i 1 i 1 operator;
pˆ   i  i .  i  i   i  i ; pˆ i pˆ j   i  i .  j  j  0
i
2

 completeness or closure relation.

 Group theoretical projection operator define as

l
Pˆ i  i  [  (i )
( R )] * ˆ
R
g R

 It will project out basis function for i-th irreducible representation from a function
which is a linear combination of basis function of all irreducible representation.

 Lets function  is a linear combination of basis function of all

irreducible representation of the point group.

  c1 (1)  c 2 ( 2 )  ...  c i ( i )

Then, Pˆ i  c i ( i )

 Lets  is an arbitrary function, then

Pˆ i  a i ( i )  If  contains basis of i-th irreducible representation Thus, using project operation one
can trace basis for irreducible
Pˆ i  0  If  does not contain basis of i-th irreducible representation
representations
 Similarly it can be shown that

Pˆ A2  0
Pˆ B1  x Please check
Pˆ B 2  y
l
Pˆ i  i  [ (i )
( R )]* Rˆ
g R

 Lets find result of operating projection operator for

irreducible representation of the point group on the
following function
  x yz

1  1
Pˆ A1    [  ( A1 ) ( R )]* Rˆ   1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz ) ( x  y  z )  z
4 R  4
 Thus, projected out basis for
1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz ) x  x  x  x  x   0 A1 irreducible representation

1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz ) y   y  y  y  y   0
1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz ) z  z  z  z  z   4 z
 Internal coordinates associated with vibrational
motions
O  
 r1 &  r2  Describes stretching of O-H bonds

q  q  Describes bending motion

H H
 For water molecule we found that two
  vibrational normal modes are of A1 types
 r1  r2
and one is B2 type.
Thus, symmetry of: vib  2 A1  B 2
 Bending mode A1
 Symmetric stretching A1 Lets try to find of these irreducible representation in terms of
 Asymmetric stretching B2 internal coordinate using projection operators Symmetric stretching

A1  1 * ˆ  1   1  r   r   r   r   [  r   r ]
P  r1    [  ( R )] R   r1  1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz )  r1
ˆ ( A1 )
1 2 2 1 1 2
4 R  4 4
(Omitting constant pre-factor)
 1 * ˆ  1  1      
P  r1    [  ( R )] R   r1  1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz )  r1   r1   r2   r2   r1   [  r1   r2 ]
ˆ B2 ( A1 )

4 R  4 4
Same result is produced with, Pˆ A1  r2   r1   r2 ; Pˆ B 2  r   r   r asymmetric stretching
2 1 2
1 1
Pˆ A1  q  1 * E  1 * C 2  1 * s ( xz )  1 * s ( yz )  q   q   q   q   q    q  Bending
4 4
 Selection rule in Electronic Transition

Examples: -MO of ethylene

 *   II  N  A   B   Anti-boning  A and B are atomic orbitals

perpendicular to the xy-plane
Z N  1/ 2
Point group of the molecule is D2h
Y    I  N  A   B   Bonding
X

Using symmetry argument justify whether   * transition is possible or not.

Ground state Excited singlet state


*
gr Oˆ  ex  0
b b
To find whether this integral is non zero or not need
symmetry of ground state and excited states

b b
  Non-degenerate eigen-functions of the Hamiltonian operator of a system act as
bases of one-dimensional representations of the systems’ point group.
Examples: -MO of ethylene

 II  N  A   B  Anti-boning  A and B are atomic orbitals

perpendicular to the xy-plane
Z N  1/ 2
Point group of the molecule is D2h
Y  I  N  A   B  Bonding

X
Actions of symmetry operation of D2h point group on the bonding -MO as:

E  N  A   B   N  A   B   1;  ( E )  1 s ( XZ ) N  A   B   N  B   A   N  A   B ;  (s ( XZ ))  1
C 2 ( Z ) N  A   B   N  B   A   N  A   B ;  ( C 2 ( Z ))  1
C 2 (Y )N  A   B   N   A   B    N  A   B ;  ( C 2 (Y ))   1
C 2 ( X ) N  A   B   N   B   A    N  A   B ;  ( C 2 ( X ))   1
E C2(Z) C2(Y) C2(X) i s(XY) s(YZ) s(XZ)
i  N  A   B   N   A   B    N  A   B ;  ( C 2 ( X ))   1 1 1 -1 -1 -1 -1 1 1
s ( XY ) N  A   B   N   A   B    N  A   B ;  (s ( XY ))   1  Mulliken symbol B1u
s (YZ ) N  A   B   N  A   B ;  (s (YZ ))  1 Thus -boning wave function of ethylene acts as a
basis of irreducible representation B1u.
  Non-degenerate eigen-functions of the Hamiltonian operator of a system act as
bases of one-dimensional representations of the systems’ point group.
Examples: -MO of ethylene

 II  N  A   B  Anti-boning  A and B are atomic orbitals

perpendicular to the xy-plane
Z N  1/ 2
Point group of the molecule is D2h
Y  I  N  A   B  Bonding

X
Actions of symmetry operation of D2h point group on the bonding -MO as:

E  N  A   B   N  A   B   1;  ( E )  1 s ( XZ ) N  A   B   N  B   A    N  A   B ;  (s ( XZ ))  1
C 2 ( Z ) N  A   B   N  B   A    N  A   B ;  ( C 2 ( Z ))   1
C 2 (Y )N  A   B   N   A   B    N  A   B ;  ( C 2 (Y ))   1
C 2 ( X ) N  A   B   N   B   A   N  A   B ;  (C 2 ( X ))   1
E C2(Z) C2(Y) C2(X) i s(XY) s(YZ) s(XZ)
i  N  A   B   N  A   B   N  A   B ;  (C 2 ( X ))  1 1 -1 -1 1 1 -1 1 -1
s ( XY ) N  A   B   N   A   B    N  A   B ;  (s ( XY ))   1  Mulliken symbol B3g
s (YZ ) N  A   B   N  A   B ;  (s (YZ ))  1 Thus -boning wave function of ethylene acts as a
basis of irreducible representation B3g.
 Using symmetry argument justify whether following transition is possible or not.

Ground state Excited singlet state

  gr* Oˆ  ex  0
b b
To find whether this integral is non zero or not need
symmetry of ground state and excited states

 Symmetry of -boning wave function of ethylene is B1u.

b b
 Symmetry of * wave function of ethylene is B3g.
Symmetry of ground state:
B1u  B1u  Ag
Symmetry of excited state:
B1u  B3 g  B 2 u

 Thus, transition is possible only if O has same

symmetry as B2u .
From character table, it is clear that electric dipole
induced transition with y-polarized light,   *
transition is symmetry allowed
Thank you
 Find matrix representation of the C2 operators using the atomic orbitals of H2O molecule
 Let us consider effect of the operator C2 on the valence shell atomic orbitals
C 21  0 .1  1 . 2  0 . 3  0 . 4  0 . 5  0 . 6 0 1 0 0 0 0
 
O C 2 2  1 .1  0 . 2  0 . 3  0 . 4  0 . 5  0 . 6 1 0 0 0 0 0
C 2 3  0 .1  0 . 2  1 . 3  0 . 4  0 . 5  0 . 6 0 0 1 0 0 0
D (C 2 )   
H H C 2 4  0 .1  0 . 2  0 . 3  1 . 4  0 . 5  0 . 6 0 0 0 1 0 0
0 0 0 0 1 0 
C 2 5  0 .1  0 . 2  0 . 3  0 . 4  1 . 5  0 . 6 
0 0 0 0 0 1 

C 2 6  0 .1  0 . 2  0 . 3  0 . 4  0 . 5  1 . 6

1s of hydrogen atom 1  1  C21  2 C 2 1 2 3  4 5 6  

1s of hydrogen atom 2  2  C22  1 0 1 0 0 0 0

 
2s of oxygen atom  3  C23  3
1 0 0 0 0 0
0 0 1 0 0 0
2px of oxygen atom  4  C24  4  1 2 3 4 5 6   
0 0 0 1 0 0
2py of oxygen atom  5  C25  5 0 0 0 0 1 0 

2pz of oxygen atom  6  C26  6 0 0 0 0 0 1 

 Find matrix representation of the C2 operators using the atomic orbitals of H2O molecule
 Let us consider effect of the operator C2 on the valence shell atomic orbitals
C 21  0 .1  1 . 2  0 . 3  0 . 4  0 . 5  0 . 6 0 1 0 0 0 0
 
O C 2 2  1 .1  0 . 2  0 . 3  0 . 4  0 . 5  0 . 6 1 0 0 0 0 0
C 2 3  0 .1  0 . 2  1 . 3  0 . 4  0 . 5  0 . 6 0 0 1 0 0 0
D (C 2 )   
H H C 2 4  0 .1  0 . 2  0 . 3  1 . 4  0 . 5  0 . 6 0 0 0 1 0 0
0 0 0 0 1 0 
C 2 5  0 .1  0 . 2  0 . 3  0 . 4  1 . 5  0 . 6 
0 0 0 0 0 1 

C 2 6  0 .1  0 . 2  0 . 3  0 . 4  0 . 5  1 . 6

1s of hydrogen atom 1  1  C21  2 Important notes:

If a basis function remains unchanged under symmetry operation contribute
1s of hydrogen atom 2  2  C22  1 one to diagonal element of representative matrix.
2s of oxygen atom  3  C23  3
If basis function change the sign without being shifted or changing
2px of oxygen atom  4  C24  4 magnitude, it contribute -1 to the diagonal elements of representative
matrix.
2py of oxygen atom  5  C25  5
2pz of oxygen atom  6  C26  6 If basis function changes to a new function or basis vector is shifted , it
contribute zero to the diagonal elements of representative matrix.
Try more examples
Selection rules for transition between vibration levels:

  *f ˆ  i  0 In case of IR spectroscopy, the electric dipole  transform as x, y, z

  *f  ind  i  0  In case of Raman , the dipole is induced dipole, polarizability

Where induced dipole is related to the

molecular polarizability as,
 ind   E
Thus, condition can be simplified as,

  *f   i  0
C5 Character table Basis Functions
C5 C 52 C 53 C 54 C 55 Linear Quadratic
D1 e e2 e3 e4 e5 z2, x2,y2,dx2-y2
D2 e2 e4 e6 e8 e10 z xy, dxy
D3 e3 e6 e9 e12 e15 x yz, dyz
D4 e4 e8 e12 e16 e20 y zx, dzx
D5 e5 e10 e15 e20 e25
 Thanks

C5 Character table Basis Functions

C5 C 52 C 53 C 54 C 55 Linear Quadratic
D1 e e2 e3 e4 e5 z2, x2,y2,dx2-y2
D2 e2 e4 e6 e8 e10 z xy, dxy
D3 e3 e6 e9 e12 e15 x yz, dyz
D4 e4 e8 e12 e16 e20 y zx, dzx
D5 e5 e10 e15 e20 e25