Chapter 5.

Molecular Symmetry
Outline
A. Introduction B. Symmetry elements and symmetry operation C. Point groups D. Applications of symmetry References 1. Catherine E. Housecroft and Alan G. Sharpe, Inorganic Chemistry, 1st Ed., Pearson Education Ltd., 2008, Chapter 4. 2. D.F.Shriver, P.W.Atkins et al, Inorganic Chemistry, 4th Ed., Oxford University Press, 2006, Chapter 7. 3. B. Douglas, D. McDaniel and J. Alexander, Concepts and Models of Inorganic Chemistry, 3r Ed., John Wiley & Sons, Inc. 1994, Chapter 3. 4.Gary L. Miessler, Donald A. Tarr, Inorganic Chemistry, Pearson Education Ltd., 2004, Chapter 4.
1

A. Introductions
Symmetry is is all around us and is present in nature and in human culture

Many Inorganic compounds also have symmetry.

F O C O F B F Cl Cl Pt CO CO

Cl Cl Co

2F Cl Cl F

F P F F F

F F S F F F

Will be useful to identify symmetry elements of molecules implications for bonding and spectroscopy

F F F F F B12H1223

F F Ru

B. Symmetry Operations and Elements

Definitions Symmetry Operation = a movement of a body such that the appearance after the operation is indistinguishable from the original appearance (if you can tell the difference, it wasn t a symmetry operation) e.g. reflection, rotation, Symmetry Element = geometrical entity with respect to which one or more symmetry operations can be carried out. e.g. could be a point, an axis or a plane

Types of Symmetry elements and operation

There are five important types of symmetry operations summarized on the right with their associated symmetry elements Symmetry element Identity* n-Fold symmetry axis Mirror plane Center of inversion n-Fold axis of improper rotation Symmetry operation None Rotation by 2/n Reflection Inversion Rotation by 2/n followed by reflection perpendicular to rotation axis Symbol E Cn I Sn

1. Identity, E.
The identity E. The identity E operation does nothing. No change in the object. May not seem like an operation at all, but is important when we consider a set of symmetry elements which form a group. ---Needed for mathematical completeness ---Every molecule has this symmetry element

2. Proper rotation, Cn
Simple rotation about an axis passing through the molecule by an angle of 360o/n. This operation is called a proper rotation (or simply rotation) and symetry element is symbolized by Cn
e.g. Water has a two-fold rotation axis (C2 operation) Rotation by 180 leaves H2O in identical orientation. We say water has a C2 rotation axis.
6

O H H 180
o

O H H

C3 Symmetry element and operations

e.g. NH3 has a C3 rotation axis. One can perform two C3 operations

Common n-fold rotation axis Cn - 360o/n rotation

Rotation rotation by 180o rotation by 120o rotation by 90o rotation by 72o fold rotation by 60o symbol

Exercise. Locate the Cn axis in the following molecules.

F O C O F B F Cl

Cl Pt Cl Cl

2-

Common n-fold rotation axis Cn - 360o/n rotation

Rotation rotation by 180o rotation by 120o rotation by 90o rotation by 72o fold rotation by 60o symbol C2 C3 C4 C5 C6

Exercise. Locate the Cn axis in the following molecules.

F O C O F B F Cl

Cl Pt Cl Cl

2-

F O C O F B F Cl

Cl Pt Cl Cl

2-

F O C O F B F Cl

Cl Pt Cl Cl

2-

10

F O C O F
C2

Cl B F Cl Pt Cl Cl

2-

F O C O F B F Cl

Cl Pt Cl Cl

2-

11

C2 C

F O C O F
C2 C2

C2

Cl Cl Pt Cl Cl

2-

F O C O F
C3

Cl B F Cl Pt Cl Cl

2-

12

C2 C

F O C O F
C2 C2

C2

Cl Cl
C2 C2

2Cl
C2

Pt Cl

C2

F O C O F
C3 C4

Cl B F Cl Pt Cl Cl

2-

13

Cl Cl
C2 ??

2Cl
Also has this C2 symmetry element?

Pt Cl

14

Cl Cl
C2 ??

2Cl
Also has this C2 symmetry element?

Pt Cl

Cl Cl Pt Cl
C4

2Cl

No. One can perform a C2 operation about the axis. This axis is the C4 axis.

15

3. Reflection (Mirror), .
Reflection of all atoms through a plane, e.g. water molecule
Note that a water molecule can be reflected by two planes. Mirror plane symmetry operation is denoted as
O H H H O H H O H H O H

Exercise. Locate planes in the following molecules.

F O C O F B F Cl

Cl Pt Cl Cl

2-

16

Answers

F C O F B F Cl

Cl Pt Cl Cl

2-

17

Answers

F C O F B F Cl

Cl Pt Cl Cl

2-

18

Answers

F C O F
F B F F

Cl B F Cl Pt Cl Cl

2-

F B F F B F F

F F B F
19

Answers

F C O F
F B F F

Cl B F Cl Pt Cl Cl

2-

Cl Cl Pt Cl Cl

2-

F B F F B F
Cl Cl Cl Cl Pt Cl Cl
20

F
Cl

Cl Pt Cl Cl Cl

Cl Pt Cl Cl

F F B F
Cl Pt Cl

Type of mirrors
F B F h F F B F F C2
C2

F F F B F v

h = plane perpendicular to principal axis v = plane includes the principal axis (d = a kind of v plane includes the principal axis, but not the outer atoms)

B F C3

d O H v
21

O C O h
C

4. Inversion (Center of Inversion), i = each point moves through a common central point to a position opposite and equidistant. Reflection of all atoms through a point. Each atom has a identical counter-part on the other side of the molecular center. e.g.
F N N F F S F F F

The inversion center I could be midway along a bond, e.g. as in N2 molecule. Or may be situated at an atomic center itself, e.g. as in SF6.
22

Question. Which of these molecules have a center of inversion? H2O, O2, NO2, CO2

O H H

N O O

C O
23

Question. Which of these molecules have a center of inversion? H2O, O2, NO2, CO2

O H H

N O O

C O

24

Question. Which of these molecules have a center of inversion? H2O, O2, NO2, CO2

O H H

N O O

C O

25

4. Improper rotation Sn. also called Rotation-Reflection

The combination, in either order, of rotating the molecule about an axis passing through it by 360o/n and reflecting all atoms through a plane that is perpendicular to the axis of rotation. Sn = Cn + h

Question. How many S4 rotation axis does a CH4 molecule have?

26

C4 H1 H2 C4 C H3 H4 h H3 H1 H2 C h H3 C H1 H2 H4

H4

27

S4

C
S4

S4

H
Three

28

Exercise. Which of the following species have a Sn axis?

F B F F Cl Cl Pt Cl Cl L L L M L L

L L L M L L Ru

29

Exercise. Which of the following species have Sn axis?

F B F
S3

Cl F Cl Pt Cl Cl

L L L M L L

L L L M L L Ru

30

Exercise. Which of the following species have Sn axis?

F B F
S3

Cl F Cl Pt Cl
S4

L Cl L L M L L

L L L M L L Ru

31

Exercise. Which of the following species have Sn axis?

F B F
S3

Cl F Cl Pt Cl
S4

L Cl L L M L
S3

L L L M L L Ru

32

Exercise. Which of the following species have Sn axis?

F B F
S3

Cl F Cl Pt Cl
S4

L Cl L L M L
S3 S5

L L L M L L Ru

33

Fa C3 Fb Fc Fa

Cla B C3 B h Fb Fc Clb C4 Pt Clc Cld Cla Pt Clb h B Fb Cla Cld Pt Clb Clc Clc Cld C4

La Lb C3 Lc La

C Ld 3 M Le Ld M Le h Lb Lc

Fc Fa

Lc La

Le M Ld
34

Lb

L L L M C4 L L L M h M L
35

L L

Ru

C5 L L

Ru

Ru

L L

Some interesting points:

S1 operation is equivalent to the mirror reflection

S2 is equivalent to a center of inversion i

36

Summary of symmetry operations and symmetry elements

37

Examples:

38

39

C. Point Groups 1. Definition.

One molecule may have more than one symmetry elements and one can perform various symmetry operations. E.g.
O H N H H H
E, C2, 2v

E, C3, 3v

The complete set of symmetry operations than can be performed on a molecule is called the symmetry group for the molecule.

40

Not accurate!

41

E, 4C3, 3C2, 3S4, 6d Td

E, 3C4, 4C3, 4S6, 3S4, i, (6+3)C2, 9, Oh 42

43

2. Characteristics of Common Point Groups

2.1. Groups of Low Symmetry

E,

E, i

44

2.2. Cn groups (n = 1, 2, )
H H N

Contain only one Cn rotational axis

B H N H H N

C3

2.3. Cnv groups Contain Cn and nv

C2v C3v

C2 d H O H

Cl

Examples

F Sb F F

v
Br

45

2.2. Cn groups (n = 1, 2, )
H H N

Contain only one Cn rotational axis

B H N H H N

C3

2.3. Cnv groups Contain Cn and nv

Cl

C2v

Examples

C2
F

F Sb F

Br

46

2.2. Cn groups (n = 1, 2, )
H H N

Contain only one Cn rotational axis

B H N H H N

C3

2.3. Cnv groups Contain Cn and nv

Cl

C2v

Examples

C3v C3
F Sb F F F

C2

Br

47

2.2. Cn groups (n = 1, 2, )
H H N

Contain only one Cn rotational axis

B H N H H N

C3

2.3. Cnv groups Contain Cn and nv

C2v C3v C3

C4
Cl

C4v

Examples

C2

F Sb F F

Br

48

How about the following compounds?

F SF 4 S F

F F F

F S F F

F F

F S F

F F

SClF 5

F F

S Cl

49

How about the following compounds?

F SF4 S F F SClF5 F F S Cl F S F F F F F S F F S F

F F

F F

F F

C2v

C4v

Cl other 3 v are not shown

50

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2h
H

Me C O X Mo R 3P O C Me X O Mo O PR3
O

O O O

O O S O O Re O

O Re O

S O

S O O
51

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2 C2h

C2

Me C O X Mo R 3P O C Me X O Mo O PR3
O

O O O

O O S O O Re O

O Re O

S O

S O O
52

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2 C2h

C3
H

C3h

Me C O X Mo R 3P O C Me X O Mo O PR3
O

O O O

O O S O O Re O

O Re O

S O

S O O
53

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2 C2h

C3
H

C3h

C3

C2

Me C O X Mo R 3P O C Me X O Mo O PR3
O

O O O

C3h

O O S O O Re O

O Re O

S O

S O O
54

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2 C2h

C3
H

C3h

C3

C2

Me C O O X Mo R 3P O
C2

O O O

C3h

O Re O

S O

C2h

Mo X O C Me

PR3

O S O

Re O

S O O
55

2.4. Cnh groups

C n + h
H Cl Cl
B H O H O

C2 C2h

C3
H

C3h

C3

C2

Me C O O X Mo R 3P O
C2

O O O

C3h

O Re O

S O
C4h C4
56

C2h

Mo X O C Me

PR3

O S O

Re O

S O O

O O O

O O O

O O O S O O Re O

O Re O

S O O
C4

O O S O O Re O

O Re O

S O

h
S O

S O O

Any other symmetry element?

57

O O O

O O O

O O O S O O Re O

O Re O

S O

O O O S O O Re O

O Re O

S O

S O O

C4
O

S O

Any other symmetry element?

O S O O O

E, I, S4

O O O S O O Re O

O Re O

S O

S O O

S4

58

2.5. D Groups
A Cn principal rotational axis is accompanied by a set of n C2 axes perpendicular to it.

Characteristic symmetry elements:

Dn groups: Cn + n C2 Dnh group: Cn + n C2 + h Dnd group: Cn + n C2 + nv

59

a). Dn groups
Cn + nC2 ()

A Cn principal rotational axis is accompanied by a set of nC2 axes perpendicular to it

C2

C2 C3 C2 D3 group
60

b). Dnh groups

Characteristic symmetry elements: Cn + nC2 + h h: horizontal mirror plane, perpendicular to the principal axis Cn. Also has n v, and maybe others too
C3 C2

Examples

Symmetry elements:

61

b). Dnh groups

Characteristic symmetry elements: Cn + nC2 + h h: horizontal mirror plane, perpendicular to the principal axis Cn. Also has n v, and maybe others too
C3 C2

Examples

h S3

Point group: D3h Symmetry elements:

E, C3, 3C2(), h, 3v, S3

62

XeF4

F F Xe F F

Symmetry elements:

63

XeF4

F F Xe F
Point group: D4h

Symmetry elements:

E, C4, 4C2(), h, 4v, + ?

64

XeF4

F F Xe F
Point group: D4h

Symmetry elements:

E, C4, 4C2(), h, 4v, S4, i

65

How about the following species?

dual relationship

[PtCl4]2- a square planar geometry C 6H 6 BF3

66

How about the following species?

D3h

dual relationship

[PtCl4]2- a square planar geometry C 6H 6 BF3

67

How about the following species?

D3h D6h

dual relationship

[PtCl4]2- a square planar geometry C 6H 6 BF3

68

How about the following species?

D3h D6h

dual relationship

D5h

[PtCl4]2- a square planar geometry C 6H 6 BF3

69

How about the following species?

D3h D6h

dual relationship

D4h D5h

[PtCl4]2- a square planar geometry C 6H 6 BF3 D6h

D3h

D3h

70

How about the following species?

D3h D6h

dual relationship

D4h D5h

[PtCl4]2- a square planar geometry C 6H 6 BF3 D6h D5h

D3h

D3h

71

72

c) Dnd group:
Characteristic symmetry elements: Cn + nC2 + v Do not have h mirror plane Examples:
R3WWR3 Point group: symmetry elements:
R R R W W R R R R W R R W R R R R R R W W R R R

Ferrocene Point group: symmetry elements:

Fe

Fe

Fe

73

c) Dnd group:
Characteristic symmetry elements: Cn + nC2 + v Do not have h mirror plane Examples:
R

R3WWR3 Point group:

R R

W W R

R R R

R W W R R

R R R

R W W R R

R R

symmetry elements:

74

c) Dnd group:
Characteristic symmetry elements: Cn + nC2 + v Do not have h mirror plane Examples: C3
R

R3WWR3 Point group: D3d

R R

W W R

R R

R W R R W

R R C2 R R

v W W

R R

S6 R W R R
symmetry elements: E, C3, 3C2(), 3v, I, S6

R R R

i R W W R R
75

R R

W R

Fe

Fe

Fe

Point group:

symmetry elements:

76

C5 v

Point group: D5d

Fe

Fe

C2

Fe

S10

Fe
symmetry elements: E, C5, 5C2(), 5v, I, S10

Fe

77

C 2 ( )
78

Dnd groups

Additional examples

square antiprism

Steggered ethane

e.g. triagular antiprism

H H

H C C C H

H H

allene

79

Dnd groups

Additional examples
Steggered ethane

e.g. triagular antiprism (D3d)

C2

C2

C3
80

Dnd groups

Additional examples
Steggered ethane

e.g. triagular antiprism (D3d)

C3 C2

C2

C2

D3d

C3
81

H H C C C
Point group:

H H

82

C2 H H H C C C H H H C2 H C2 H H C2 H H v H

Point group: D2d

C2 H

H H H

C2 H

H H H
83

Point group:

84

Point group: D4d

C4 B' C' D'

A'

C2 A B C v

85

2.6. Sn groups (n = even only because one gets Cnh when n = odd S1 = Cs S2 = Ci When n = odd, Sn Cnh. Thus n can only be even

Me

H H

Me
XB NR BX NR BX N R
86

RN

H Me

Me H

B X

C4 H Me H Me C4 h h Me H H Me Me H H Me

H Me

Me

H Me

Me

H Me

Me

Point group: S4 Symmetry elements?: S4

87

C4 H Me H Me C4 h h Me H H Me Me H H Me

H Me

Me

H Me

Me

H Me

Me

Point group: S4

88

C4 XB RN XB NR C4 XB BX BX RN NR RN XB BX BX h NR XB h RN XB BX NR RN BX NR

NR RN

Point group: S4

89

2.7. High symmetry point groups

a) Tetrahedral point groups Td point group Characteristic symmetry elements: 4C3 + 3C2 (e.g. CH4, SiCl4, etc)

Cl Si Cl Cl Cl
Any other symmetry elements?

In addition there are molecules with Th point group. Th point group: T + I (rare)
90

2.7. High symmetry point groups

a) Tetrahedral point groups Td point group Characteristic symmetry elements: 4C3 + 3C2 (e.g. CH4, SiCl4, etc) C3

Cl Si Cl
C3

C3

C3

Cl Cl

Any other symmetry elements?

C2 C2 C2

In addition there are molecules with Th point group. Th point group: T + I (rare)
91

2.7. High symmetry point groups

a) Tetrahedral point groups Td point group C3 Characteristic symmetry elements: 4C3 + 3C2 (e.g. CH4, SiCl4, etc) C3

Cl Si Cl
C3
C2 C2 C2

C3

Cl Cl

Any other symmetry elements?

S4 S4 S4

In addition there are molecules with Th point group. Th point group: T + I (rare)

92

b) Octahedral point groups Oh point group: Characteristic symmetry elements 3C4 e.g. SF6 Additional symmetry elements E, 4C3, 4S6, 3S4, i, 6C2, 9

C4

Icosahedral point groups Ih point group: Characteristic symmetry elements 6C5 + i

C5

Additional symmetry elements: E, 10C3, 6S10, 10S6, 15C2, 15, Ih

93

Summary
T group: 4C3 O group: 3C4 I group: 6C5

94

3. Identification of point groups.

To identify a molecules point group, a list of symmetry elements could be made and then compare them with list characteristic of each point group. e.g. To what point groups do H2O and NH3 belong?
O H H H N H

(a) H2O possesses the following symmetry elements: E, C2, 2v. The set of elements (E, C2, 2v) corresponds to the group C2v. (b) NH3 possesses following symmetry elements: E, C3, 3v. The set of elements (E, C3, 3v) corresponds to the group C3v.
95

Alternatively, one can use set of rules for assigning the point group follow a flow chart (see below).
Notes: The symmetry elements used to identify a point group (as shown in the chart) do not form a complete set of symmetry elements for the molecule under consideration

96

Exercises:
Give the point group of following molecules.
(a) Mer-[Fe(CN)3Cl3]3(c) Mo(CN)84(e) Mn2(CO)10 (g) 1,5-dibromonaphthalene (b) IF7 (d) trans-HClC=CClH (f) P4

97

Answers
N C (a) N C Cl Cl Fe Cl 3Low symmetry? High symmetry (Td, Oh, Ih)? Highest Cn? Any C2 Cn? Any h? Any v?

C N

N C N C Cl

Cl Fe Cl

N C N C C2 Cl

Cl Fe Cl

N C N C Cl

C N

C N

Cl Fe Cl

C N
98

Answers
N C (a) N C Cl Cl Fe Cl 3Low symmetry? No High symmetry (Td, Oh, Ih)? No Highest Cn? C2 Any C2 Cn? No Any h? No Any v? Yes C2v

C N

N C N C Cl

Cl Fe Cl

N C N C C2 Cl

Cl Fe Cl

N C N C Cl

C N

C N

Cl Fe Cl

C N
99

F F (b) F I F F F F
Low symmetry? High symmetry (Td, Oh, Ih)? Highest Cn? Any C2 Cn? Any h?

F F F I F F F F F F

F F I F F
100

C5

F F (b) F I F F F F
Low symmetry? No High symmetry (Td, Oh, Ih)? No Highest Cn? C5 Any C2 Cn? Yes Any h? Yes D5h

F
h

F F F F F F I F F
101

F I

F F
C2

NC NC NC Mo CN CN CN

Low symmetry? High symmetry (Td, Oh, Ih)? Highest Cn? Any C2 Cn? Any h? Any d (or v)?

NC
NC NC NC Mo CN

CN
NC NC NC Mo CN CN CN CN

CN

NC

CN

NC

CN

102

C4
NC NC NC Mo CN CN CN

Low symmetry? No High symmetry (Td, Oh, Ih)? No Highest Cn? C4 Any C2 Cn? Yes Any h? No Any d (or v)? Yes D4d

NC

CN

NC NC CN NC Mo CN CN NC

NC CN NC Mo CN CN

C4 B' C' D'

A'

C2 A B C v
NC

CN

NC

CN

103

(d)

H Cl

Cl H
(e)OC OC

CO Mn OC CO

CO CO Mn CO CO CO

P (f) P P P
(g)

Cl

Cl
104

(d)

H Cl
C2h

Cl H
(e)OC OC

CO Mn OC CO

CO CO Mn CO CO CO

P (f) P P P
(g)

Cl

Cl
105

(d)

H Cl
C2h

Cl H
(e)OC OC

CO Mn OC CO

CO CO Mn CO
D4h

CO CO

P (f) P P P
(g)

Cl

Cl
106

(d)

H Cl
C2h

Cl H
(e)OC OC

CO Mn OC CO

CO CO Mn CO
D4h

CO CO

P (f) P P
Td

Cl (g)

Cl
107

(d)

H Cl
C2h

Cl H
(e)OC OC

CO Mn OC CO

CO CO Mn CO
D4h

CO CO

P (f) P P
Td

Cl (g)
C2h

Cl
108

Additional examples
C60 dodecahedron

109

110

C60 6 C5

Th

111

dodecahedron

112

dodecahedron 6 C5

Th

113

114

Point group?

115

Point group?

Oh

116

C4

C4 C4

Oh E, 3C4, 4C3, 4S6, 3S4, i, 6C2, 9, Oh

Oh

117

C4

C4 C4

Oh

Oh

Oh

E, 3C4, 4C3, 4S6, 3S4, i, 6C2, 9, Oh

118

Dual polyhedra
Every polyhedron has a dual polyhedron with faces and vertices interchanged. The tetrahedron is self-dual (i.e. its dual is another tetrahedron). The cube and the octahedron form a dual pair. The dodecahedron and the icosahedron form a dual pair.

Ih Ih Ih

Oh

119

Point group?

120

Point group?

Td

Oh

Oh

Ih

Ih
121

Summary:

Some typical shapes of point groups

122

123

D. Applications of symmetry
1. Molecular polarity A polar molecule is a molecule with a permanent electric dipole moment.

Symmetry consideration: a molecule (1) can not have a permanent dipole if it has an inversion center. (2) cannot have a permanent dipole perpendicular to any mirror plane. (3) cannot have a permanent dipole perpendicular to any axis of symmetry.
+
C2

F F Xe F F
+

The presence of a mirror plane or a C2 axis rules out a dipole in the direction shown.

124

z F F

C4 F F F F

C3 B F

Xe

Cannot have a dipole in the xy plane

125

Conclusion
Conclusion: Molecules having both a Cn axis and a perpendicular C2 axis or h cannot have a dipole in any direction. -Molecules belonging to any D, T, O or I groups cannot have permanent dipole moment. Molecules can not have a permanent dipole if it has an inversion center - some Cnh, Sn groups Exercises: Which of the following molecules are polar?

F Fe F F S Cl

F F F S F

F F

126

Conclusion
Conclusion: Molecules having both a Cn axis and a perpendicular C2 axis or h cannot have a dipole in any direction. -Molecules belonging to any D, T, O or I groups cannot have permanent dipole moment. Molecules can not have a permanent dipole if it has an inversion center - some Cnh, Sn groups Exercises: Which of the following molecules are polar?

F Fe F F S Cl

F F F S F

F F

D5d, no

C4v, yes

C2v, yes

127

2. Molecular chirality ()
A chiral molecule () is a molecule that is distinguished from its mirror image in the same way that left and right hands are distinguishable

Symmetry consideration: A molecule that has no axis of improper rotation (Sn) is chiral. Remember, Sn including S1 = and S2 = i Conclusion: a molecule lack of Sn (including , i ) are chiral.
128

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl F F F (b) S F F F

Me

H H

Me

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

H Me

Me H
129

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl

F F (b) S F

F F

Me

H H

Me

Has , not chiral

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

H Me

Me H
130

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl

F F (b) S F

F F

Me

H H

Me

Has , not chiral

Has , not chiral

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

H Me

Me H
131

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl

F F (b) S F

F F

Me

H H

Me

Has , not chiral

Has , not chiral

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

, I and Sn =>chiral

H Me

Me H
132

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl

F F (b) S F

F F

Me

H H

Me

Has , not chiral

Has , not chiral

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

, I and Sn =>chiral

H Me

Me
Has S4 not chiral

H
133

Exercises: Which of the following molecule is chiral?

F (a) F F S Cl

F F (b) S F

F F

Me

H H

Me

Has , not chiral

Has , not chiral

N
N (c) N Co N N N N (d)
(e) The skew form of H2O2

, I and Sn =>chiral

H Me

Me
Has S4 not chiral

, I and Sn =>chiral
134

3. Symmetries of Orbitals
Diatomic species

Other labels

2p*

2p*

2p

2p 2s*

Based on symmetry in relation to rotation.

2s O2 and F2
135

Orbital labels for polyatomic species

z x O y H O H 6 H 5 4 2pz 2py 2px 3 2 1 H

z x O y H O H H 2b2 1b1 2pz 2py 2px 2a1 1b2 1a1

136

3a1

2s

2s

MO of BH3
z
5 4

x 2e' 2a1' 2py 2px 2pz a2" e' a1' 2s 1a1' 1a2" 1e'

2py 2px 2pz

2 2s 1

The more elaborated labels are based on the behavior of orbitals under all operations, which can be assigned by referring to character table.
137

Character,

Character: a number indicating (relating) how an object is affected by a symmetry operation.
H C2 O O H H H (C2) = -1

+1 -1 0

no change. change sign. move to a new place.

C2 O

O H H H

(C2) = 1

H C2 O H

O H H H

(C2) = 0

138

Orbital Symmetry, Consider pz in C2v

Under C2v, we have E, C2, 2v

(E) = +1 C2(z)

y (C2(z)) = +1 x v(xz) v(yz)

O H H

(v(xz)) = +1

(v(xz)) = +1
139

Orbital Symmetry, Consider px in C2v

z E + x v(xz) y

C2(z)

(E)

= +1 +
(C2(z))

v(yz) +

= -1

(v(yz))

= -1

(v(xz)) = +1
140

Orbital Symmetry, Consider px in C2v

z E x + y

+ C2(z)

(E) = +1 + (C2(z)) = -1 + ((yz)) = +1

v(yz) v(xz) + -

(v(xz)) = -1
141

Summary C2 (px) = - (px) xz (px) = (px) yz (px) = - (px) C2 (py) = - (py) xz (py) = - (py) yz (py) = (py) C2 (pz) = (pz) xz (pz) = (pz) yz (pz) = (pz)

C2 (dxz) = - (dxz) xz (dxz) = (dxz) yz (dxz) = - (dxz) C2 (dyz) = - (dyz) xz (dyz) = - (dyz) yz (dyz) = (dyz)

142

Summary C2 (px) = - (px) xz (px) = (px) yz (px) = - (px) C2 (py) = - (py) xz (py) = - (py) yz (py) = (py) C2 (pz) = (pz) xz (pz) = (pz) yz (pz) = (pz)

-1 1 -1

C2 (dxz) = - (dxz) xz (dxz) = (dxz) yz (dxz) = - (dxz) C2 (dyz) = - (dyz) xz (dyz) = - (dyz) yz (dyz) = (dyz)
-1 1 -1 -1 -1 1

-1 -1 1

1 1 1
143

Character table: summary of characters

Each point group has a character table associated with it.

144

Descriptions of Character table

d orbitals p orbitals

145

An Example
Name of point group Symmetry operation Function or basis

labels of symmetry species

Character

Symmetry species and atomic orbital s orbital: the first one px, py,pz =>x,y,z dxy,dxz,dyz => xy,xz,yz dx2-y2=>x2-y2 dz2 => z2, 2z2-x2-y2
146

Molecular orbitals may have the same symetry properties as atomic orbitals, e.g.

C2 (py) = - (py) xz (py) = - (py) yz (py) = (py)

C2 ( xz ( yz (

)=-( )=-( )=( )

) )

147

b2,

148

More complicated cases

H B H H

H C3 H B
y x C3 x H y H

H B H
149

H B H

H B H H

H C3 H B H

x' y' z'

x C3 y z
y x'

C3 (x,y):
x

-1/2 3/2

3/2 -1/2

y' z (z')

C3(z):[1]

1 E (x, y): 0

0 1

E(z): [1]
150

Character () and matrix

x' = [1]x x' = [-1]x

=1 = -1 b c e f h i x y z

x' y' z'

a d g

= a+ e+ i

151

C3 (x,y):

-1/2 3/2

3/2 -1/2

1 E (x, y): 0

0 1

(C3) = -1

(C3) = 2

C3(z):[1]
(C3) = 1

E(z): [1]
(C3) = 1

152

Labels for symmetry species

153

1: symmetric with regard to mirror (v) 2: antisymmetric with regard to mirror (v)
154

155

156

Real examples

g z y u g u
157

H 2O

z x O y H O H H 2b2
z y x

3a1

1b1 2pz 2py 2px a1 b2 b1 a1 2s 2a1 1b2 1a1

158

Symmetry labels of the LGOs?

H 2O

z x O
z y x

H H 2b2 1b1 H
b2

3a1

2pz 2py 2px a1 b2 b1 a1 2s

2a1 1b2 1a1

a1

Symmetry labels of the LGOs?

159

BH3

y x z 2e' 2a1' 2py 2px 2pz a2" e' a1' 2s 1a1'

160

1a2" 1e'

y x z 2e' 2a1' 2py 2px 2pz a2" e' a1' 2s 1a1'

161

BH3

1a2" 1e'

NH3
H

N H

162

NH3
3a1
2e

z y x
y
e

x 2a1 z a1

1e

s a1

Symmetry labels of the LGOs?

H H H

1a1 N
163

NH3
3a1
2e

z y x
y
e

e
2a1

x z a1

a1

1e

s a1

Symmetry labels of the LGOs?

H H H

1a1 N
164

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6

L L

L L

L p L s M L L

165

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6

L L

L L

symmetry labels for AOs?

p L s

L M L L

166

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6

L L

L L

symmetry labels for AOs? t2 a1 t2

p L s

L M L L

e symmetry labels for MOs?

167

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6

L L

L L
3t2

symmetry labels for AOs? t2 a1 t2

p s

L M L L L

2a1 2t2

1e 1t2
168

e symmetry labels for MOs?

1a1

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6

L L

L L
3t2

symmetry labels for AOs? t2 a1 t2

p s

L M L L L

2a1 2t2

1e 1t2

t2

e symmetry labels for MOs?

169

1a1

a1

L L L

L L

M
L

symmetry labels for AOs and LGOs?

p
s

170

L L L

L L

M
L

symmetry labels for AOs and LGO? t1u a1g t2g eg symmetry labels for MOs?
p
s

eg t1u

a1g
171

L L L

L L

M
L

symmetry labels for AOs and LGOs? t1u a1g t2g

d

2t1u
p
s

2a1g 2eg

eg t1u

1t2g 1eg 1t1u 1a1g a1g

172

eg symmetry labels for MOs?

Summary of Chapter 5 Types of Symmetry elements and operation E, Cn, , I, Sn Characteristics of Common Point Groups C1, Cs, Ci, Cn, Cnv, Cnh, Dn, Dnh, Dnd, Td, Oh, Ih Applications Polarity, chirality, symmetry labels of orbitals
173