Lecture 38: Selection Rules The material in this lecture covers the following in Atkins. 15 Molecular Symmetry 15.

5 Vanishing integrals and orbital overlaps (a) The criteria for vanishing integrals (b) Orbitals with nonzero overlaps (c) Symmetry-adapted linear combinations 15.6 Vanishing integrals and selection rules Lecture on-line Selection Rules (PowerPoint) Selection Rules (PDF) Handouts for this lecture

Character Table

C3 v

Symmetry operations in the same class are related to one another by the symmetry operations of the group. Thus, the three mirror planes shown here are related by threefold rotations : C3v=v and the two rotations shown here are related by reflection in v. vC3=C3-1

Character Table

C3 v

The dimension is 6 since we have 6 elements.

We have three different symmetry representations as we have three different classes of symmetry elements

Character Table

C3 v

The pz orbital does not change

-1 with E, C3 , C3 v , 'v , "v The symmetry rep. is A1
Y

py px does change
-1 with E, C3 , C3 v , ' v , "v
Y

Character Table

C3 v

px

p' x

p' ' x

-1 Epx = p x ; C3p x = p' x ; C3 p x = p"x

-1 Ep y = p y ; C3p y = p' y ; C3 p y = p"y
Y Y Y

py

p' y

p' ' y

Character Table

C3 v

1 0 p x p y D(E) = p x p y 0 1 The trace is 2 which is also the 3 1 dimension of 2 1 ) = p p 2 px p y D(C3 the representation x y 3 1 2 2

(px

p y D(C3 ) = p x

3 1 py 2 2 3 1 2 2

The trace is - 1 for both matrices

Character Table

C3 v

(px
(
)

p y D( v ) = p x

1 0 py 0 1

3 1 2 p x p y D('v ) = p x p y 2 3 1 2 2 3 1 2 p x p y D(" ) = p x p y 2 v 3 1 2 2

The trace is - 1 for both matrices

Constructing Linear combinations Character Table How are they constructed

a1

ex

a2

ey

Typical symmetry -adapted linear combinations of orbitals in a C 3v molecule.

Character Table Constructing Linear combinations

SC

SA

SB

3v
Original basis SA SB SC SA SB SC SB SC SA SB SB SC SA SC S A S A SC SB SA SC SB
Construct a table showing the effect of each operation on each orbital of the original basis To generate the combination of a Specific symmetry species, take Each column in turn and (I) Multiply each member of the Column by the character of the Corresponding operator

E C+ 3 C3 v v' v"

Character Table Constructing Linear combinations

SA SC SB

3v
For A1 :
Original basis SA SB SC 1SA 1SB 1SC 1SB 1SC 1SA 1SB 1SB 1SC 1SA 1SC 1SA 1SA 1SC 1SB 1SA 1SC 1SB
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order 1 a1 = (SA + SB + SC ) 3

E
C3 v v' v"

C+ 3

Character Table

Constructing Linear combinations

SC

SA

SB

3v
For A 2 :
Original basis SA SB SC 1SA 1SB 1SC 1SB 1SC 1SA 1SC 1SA 1SB - 1SA - 1SC - 1SB - 1SB - 1SA - 1SC - 1SC - 1SB - 1SA
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

E
C3 v v' v"

C+ 3

a2 = 0

Character Table

Constructing Linear combinations

SC

SA

SB

3v
For E :
Original basis SA SB SC 2SA 2SB 2SC - 1SB - 1SC - 1SA - 1SC 0 SA 0 SB 0 SC - 1SA 0 SC 0 SA 0 SB - 1SB 0 SB 0 SC 0 SA
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

E
C3 v v' v"

C+ 3

1 1 = (2SA SB SC ) 6 1 2 = (2SB SA SC ) 6 1 3 = (2SC SA SB ) 6

Character Table

Constructing Linear combinations

1 1 1 = (2SA SB SC ) 2 = (2SB SA SC ) 6 6 1 3 = (2SC SA SB ) 6 Any of the functions 1, 2 , and 3 can be expressed in terms of the two other (linear dependence)

3v

Linear independent solutions : 1 1. Any of the functions 1 = I (2SA SB SC ) 6 1 2. Difference of other two : II = (SA SB ) 2

Character Table

3v

Molecular orbitals of NH3

a1

ex

ey

a1

a1

ex
ey

ex

ey

Character Table

Structure of character table

Orbitals of the same symmetry species may have non-vanishing overlap. This diagram illustrates the three bonding orbitals that may be constructed from (N2s, H1s) and (N2p, H1s) overlap in a C3v molecule. (a) a1; (b) and (c) the two components of the doubly degenerate e orbitals. (There are also three antibonding orbitals of the same species.)

Character Table Constructing Linear combinations

3v
+

2p A -

2p B - 2p C +

E
C3 v v' v"

Original basis 2pA 2pB 2pC 2pA 2pB 2pC 2pB 2pC 2pA 2pB - 2pB - 2pC - 2pA 2pC 2pA - 2pA - 2pC - 2pB - 2pA - 2pC - 2pB

Construct a table showing the effect of each operation on each orbital of the original basis To generate the combination of a Specific symmetry species, take Each column in turn and (I) Multiply each member of the Column by the character of the Corresponding operator

C+ 3

Character Table Constructing Linear combinations

+

2p A -

2p B - 2p C +

3v
For A1 :
Original basis 2pA 2pB 2pC 2pA 2pB 2pC 2pB 2pC 2pA 2pB - 2pB - 2pC - 2pA 2pC 2pA - 2pA - 2pC - 2pB - 2pA - 2pC - 2pB
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

E
C3 v v' v"

C+ 3

1 a 1 = ( 2 p A + 2 p B + 2 pC 6 2 p A 2 p B 2 pC ) = 0

Character Table Constructing Linear combinations

+

2p A -

2p B - 2p C +

3v
For A 2 :
Original basis 2pA 2pB 2pC 2pA 2pB 2pC 2pB 2pC 2pA 2pC 2pA 2pB 2pA 2pC 2pB 2pB 2pA 2pC 2pC 2pB 2pA
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

E
C3 v v' v"

C+ 3

1 a 2 = ( 2 p A + 2 p B + 2 pC + 6 2 p A + 2 p B + 2 pC ) = 1 ( 2 p A + 2 p B + 2 pC ) 3

Character Table Constructing Linear combinations

+

2p A -

2p B - 2p C +

3v
For E :
Original basis 2pA 2pB 2pC 2pA 2pB 2pC - 2pB - 2pC - 2pA - 2pC - 2pA - 2pB 0 0 0 0 0 0 0 0 0
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

E
C3 v v' v"

C+ 3

1 e 1 = ( 2 ( 2 p A ) 2 p B 2 pC ) 6 1 e 2 = ( 2 ( 2 p B ) 2 p A 2 pC ) 6 1 e 3 = ( 2 ( 2 pC ) 2 p A 2 p B ) 6

Character Table

Constructing Linear combinations

2p A +

1 1 1 = ( 2 ( 2 p A ) 2 p B 2 pC ) 2 = ( 2 ( 2 p B ) 2 p A 2 pC ) 6 6 1 + 3 = ( 2 ( 2 pC ) 2 p A 2 p B ) 6 - 2p C Any of the functions 1, 2 , and 3 can be expressed in terms of the two other (linear dependence)

2p B +

3v

Linear independent solutions : 1 1. Any of the functions 1 = I ( 2( 2pA ) 2pB 2pC ) 6 1 2. Difference of other two : II = ( 2pA 2pB ) 2p A 2 2p A
+ 2p B + 2p C + + 2p C + 2p B

Character Table

Vanishing integrals and selection rules Expectation value We have that an expectation value with regard to the operator O

is given by : < O > = Odv

For O = 1

we have

< 1 > = dv = 1

Thus must transform as A1

Thus for < O > = Odv to be different from zero

O must transform as A1

Vanishing integrals and selection rules r r r r The dipole operator is given by : = e[ xe x + y e y + z e z ]

Character Table

For C1 x,y, and z all belong to totally symmetric rep

For Ci x,y,and z do not belong to totally symmetric rep

F Br I 0 For Cs x,y, belong to totally symmetric rep Cl

Cl C C

Cl

Quinoline 0 in plane

Trans CHCl=CHCl =0 inversion

Character Table

Vanishing integrals and selection rules

The dipole operator is given by :

r r r r = e[ xe x + y e y + z e z ]

For Cn and Cnv the z components belongs to totally symmetric rep

For cnh all components different from totally symmetric rep

Character Table

Vanishing integrals and selection rules

The dipole operator is given by :

For higher symmetries :

r r r r = e[ xe x + y e y + z e z ]

Oh

Td

Dnd Dnh

No dipole

Character Table Vanishing integrals and selection rules Optical transitions The intensity of the optical 2b2 transition of electron from orbital 1 to 2 is 2a1 related to the transition dipole integral :
1b1 1b2 1a1

r r < >= 1 1dv r = e x 1 x 1dv r + e y 1 y 1dv r + e z 1 z 1dv

Let us consider H2O

.. and the transition 1b1 2a1

Character Table Vanishing integrals and selection rules Optical transitions y component
r r < >= 1 1dv r = e x 1 x 1dv r + e y 1 y 1dv r + e z 1 z 1dv
X component E C2 v v ' 1 [1b1] 2 [2a1] x 1x 2 1 -1 1 -1 1 1 1 1 1 -1 1 -1 1 1 1 1

E C2 v v ' 1 [1b1] 2 [2a1] y 1y 2 1 -1 1 -1 1 1 1 1 1 -1 -1 1 1 1 -1 -1 y component E C2 v v ' 1 [1b1] 2 [2a1] z 1y 2 1 -1 1 -1 1 1 1 1 1 -1 1 1 1 -1 1 -1

The polarizations of the allowed transitions in a C2v molecule. The shading indicates the structure of the orbitals of the specified symmetry species. The perspective view of the molecule makes it look rather like a door-stop; however, from the side, each `door-stop' is in fact an isosceles triangle.

What you should learn from this lecture

1.You should be able with the help of a character tavle to decide which components are different fom zero in : r r < >= 1 1dv r = e x 1 x 1dv r + e y 1 y 1dv r + e z 1 z 1dv