Lecture 37: Symmetry Orbitals The material in this lecture covers the following in Atkins.

15 Molecular Symmetry Character Tables 15.4 Character tables and symmetry labels (a) The structure of character tables (b) Character tables and orbital degeneracy (c) Characters and operators (d) The classification of linear combinations of orbitals 15.5 Vanishing integrals and orbital overlaps (a) The criteria for vanishing integrals (b) Orbitals with nonzero overlaps (c) Symmetry-adapted linear combinations Lecture on-line Symmetry Orbitals (PowerPoint) Symmetry Orbitals (PowerPoint) Handouts for this lecture

Character Table

Structure of character table

2v

One dimensional irreducible representations have the character 1 for E. They are termed A or B. A is used if the character of the principle rotation is 1. B is used if the character of the principle rotation is -1 A1 has the character 1 for all operations

Character Table

Structure of character table

Td

C3

C2

C3

Irreducible representations with dimension 2 are denoted E Irreducible representations with dimension 3 are denoted T Number of symmetry species (irreducible representations) = Number of classes

C3

C3

Character Table

Structure of character table

2v

A px orbital on the central atom of a C2v molecule and the symmetry elements of the group. Epx = 1px; C2px = -1 px vpx = 1px; v px = -1 px The irrep. is B 1 and The symmetry b1

Character Table

Structure of character table

2v

C2

A py orbital on the central atom v' of a C2v molecule and the symmetry elements of the group. Epy = 1py; C2py = -1 py vpy = - 1py; v py = 1 py The irrep. is B 2 and The symmetry b2

+ +

Character Table

Structure of character table

2v

C2

+ -

A pz orbital on the central atom v' of a C2v molecule and the symmetry elements of the group. Epz = 1pz; C2pz = 1 pz vpz = 1pz; v pz = 1 pz The irrep. is A1 and The symmetry a1

Character Table

Structure of character table

2v

C2

v v'

+ + - + +

A dxy orbital on the central atom of a C2v molecule and the symmetry elements of the group. Edxy = 1dxy ; C2dxy = 1 dxy vdxy = -1dxy ; v dxy = - 1 dxy The irrep. is A2 and The symmetry a2

Character Table

Structure of character table

2v

C2

terminal atoms v' of a C2v molecule and the symmetry elements of the group. E 1s+ = 1 1s+ ; C2 1s+ = 1 1s+

-A 1s+ orbital on the two

+ + +

v 1s+ = 1 1s+ ; v 1s+ = 1 1s+ The irrep. is A1 and The symmetry a1

Character Table

Structure of character table

2v

C2

A 1s- orbital on the two terminal atoms v' of a C2v molecule and the symmetry elements of the group.
E 1s- = 1 1s- ; C2 1s- = -1 1sv 1s- = -1 1s- ; v 1s- = 1 1sThe irrep. is B 2 and The symmetry b2

+ -+

Character Table

Structure of character table

2v

C2

v' A 2p- orbital on the two terminal atoms of a C2v molecule and the symmetry elements of the group.
E 2p- = 1 2p- ; C2 2p- = 1 2pv 2p- = -1 2p- ; v 2p- = -1 2pThe irrep. is A2 and The symmetry a2

+ -+

Character Table

Structure ofof character table Structure character table

I = s1s2dv

The value of an integral I (for example, an area) is independent of the coordinate system used to evaluate it. That is, I is a basis of a representation of symmetry species A1 (or its equivalent).

Character Table

Structure of character table I = C2 1s + (1)2p y (1)dv = I = 1s + (1)2p y (1)dv =

z
2py
Y

I = [C2 1s + (1)][C2 2p y (1)][C2dv ] =

I = 1s + (1)[ 2p y (1)][dv ] = I = 1s + (1)2p y (1)dv = I
z
2py
Y

1s+= 1s1 +1s2

1s+= 1s1 +1s2

This is only possible if I = 0

Character Table

Structure of character table

I = 1s (1)2pz (1)dv =

I = C2 1s (1)2pz (1)dv = I = [C2 1s (1)][C2 2pz (1)][C2dv ] = I = [ 1s (1)]2pz (1)dv =

z
2pz
Y

I = 1s (1)2pz (1)dv = I
z
2pz
Y

1s-= 1s1 -1s2

1s-= 1s1 -1s2

This is only possible if I = 0

Character Table

Structure of character table

We must have in general I = O f1f2dv = If c 1 (Of1)(Of2 )dv = I= 0 c f1f2dv with c = 1

General procedure for determining the symmetry of product f1f2

1. Decide on the symetry species of the Individual functions f1 and f2 by reference to the character table, and write their characters in two rows in the same same order as in the table

Character Table

Structure of character table

I = 1s + (1)2p y (1)dv
z
2pz
Y

1. Decide on the symmetry species of the individual functions f1 and f2 by reference to the character table, and write their characters in two rows in the same same order as in the table 2. Multiply the numbewrs in each column, Writing the results in the same order 3. The new character must be A1 For the integral to be non-zero

1s+= 1s1 +1s2

2py 1 -1 1s+ 1 1 2py1s+ 1

-1 1

1 1 1

-1 -1

The symmetry species is B2

Character Table

Structure of character table

I = 1s (1)2p y (1)dv
z
2pz
Y

For the integral

I = f1f2dv

1s-= 1s1 -1s2

2py 1 -1 -1 1s- 1 -1 -1 2py1s- 1 1 1

1 1 1

It should be clear that the above procedure only provide a A1 character if f1 and f2 belongs to the same sym. representation

The symmetry species is A1

Character Table

Structure of character table

py
pz
A1 B2

px
B1

2pz overlaps (interacts) with 1s+

1s+
A1

1s
B2

2p y overlaps (interacts) with 1s-

Character Table

Structure of character table

2v

The character table of a group is the list of characters of all its irreducible representations. Names of irreducible representations: A1,A2,B1,B2. Characters of irreducible representations

Character Table

Structure of character table Appendix 1

3v

I = xyf( x, y )dxdy f( x, y ) = 1 inside triangle; f( x, y ) = 0 outside triangle

The integral of the function f = xy over the tinted region is zero. In this case, the result is obvious by inspection, but group theory can be used to establish similar results in less obvious cases.

Character Table

Structure of character table

Appendix 1

3v

I = xyf( x, y )dxdy f( x, y ) = 1 inside pentagon; f( x, y ) = 0 outside pentagon

The integration of a function over a pentagonal region.

Character Table

How are they constructed

Constructing Linear combinations

b1

a1

ex
a2

a2

ey
Two symmetry-adapted linear combinations of the p-basis orbitals. The two combinations each span a one-dimensional irreducible representation, and their symmetry species are different.

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

Character Table

Constructing Linear combinations C2

C2 v
v'

1s1

1s 2 +
Original basis 1S1 1S2 1S1 1S2 1S2 1S1 1S2 1S1 1S1 1S2
For A1 :

E C2 v v'

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

Character Table

Constructing Linear combinations C2

C2 v
v'

1s1

1s 2 +
Original basis 1S1 1S2 1S1 1S2 1S2 1S1 1S2 1S1 1S1 1S2

E C2 v v'

(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

For A1 :

1 1 1 = (1s1 + 1s 2 + 1s 2 + 1s1 ) = (1s1 + 1s 2 ) 4 2 1 1 '1 = (1s 2 + 1s1 + 1s1 + 1s 2 ) = (1s1 + 1s 2 ) 4 2

Character Table

Constructing Linear combinations C2

C2 v
v'

1s1

1s 2 +
Original basis 1S1 1S2 1S1 1S2 1S2 1S1 1S2 1S1 1S1 1S2

E C2 v v'

(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

For A 2 :

1 1 = (1s1 + 1s 2 1s 2 1s1 ) = 0 4 1 '1 = (1s 2 + 1s1 1s1 1s 2 ) = 0 4

Character Table

Constructing Linear combinations C2

C2 v
v'

1s1

1s 2 +
Original basis 1S1 1S2 1S1 1S2 1S2 1S1 1S2 1S1 1S1 1S2

E C2 v v'

(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

For B1 :

1 1 = (1s1 1s 2 + 1s 2 1s1 ) = 0 4 1 '1 = (1s 2 1s1 + 1s1 1s 2 ) = 0 4

Character Table

Constructing Linear combinations C2

C2 v
v'

1s1

1s 2 +
Original basis 1S1 1S2 1S1 1S2 1S2 1S1 1S2 1S1 1S1 1S2

E C2 v v'

(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

For B2 :

1 1 1 = (1s1 1s 2 1s 2 + 1s1 ) = (1s1 1s 2 ) 4 2 1 1 '1 = (1s 2 1s1 1s1 + 1s 2 ) = (1s 2 1s1 ) 4 2

Character Table

Constructing Linear combinations C

2

C2 v
v'

+ + 2pA x

+ +

Original basis 2pA x E C2 v v' 2pA x 2pB x 2pB x

2pB x
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

- 2pB - 2pA x x 2pB 2pA x x - 2pA - 2pB x x

1 1 For A 2 : 1 = ( 2pA 2pB 2pB + 2pA ) = ( 2pA 2pB ) x x x x x x 4 2 ' = 1 ( 2pB 2pA 2pA + 2pB ) = 1 ( 2pB 2pA ) 1 x x x x x x 4 2

Character Table

Constructing Linear combinations C

2

C2 v
v'

+ + 2pA x

+ +

Original basis 2pA x E C2 v v' 2pA x 2pB x 2pB x

2pB x
(I) Multiply each member of the Column by the character of the Corresponding operator (2) Add and divide by group order

- 2pB - 2pA x x 2pB 2pA x x - 2pA - 2pB x x

1 1 For B1 : 1 = ( 2pA + 2pB + 2pB + 2pA ) = ( 2pA + 2pB ) x x x x x x 4 2 ' = 1 ( 2pB + 2pA + 2pA + 2pB ) = 1 ( 2pB + 2pA ) 1 x x x x x x 4 2

What you should learn from this course 1. Be able to assign symmetries to orbitals from character tables. 2. Be able to use character tables to determine whether the overlap between two functions might be different from zero. 3. Be able to use character table to construct symmetry orbitals as linear combination of symmetry equivalent atomic orbitals