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

2

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

I

F F Ru

reflection.g. it wasn t a symmetry operation) e. rotation. – could be a point. 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.g.B. an axis or a plane 4 . … Symmetry Element = geometrical entity with respect to which one or more symmetry operations can be carried out. e.

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 2π/n Reflection Inversion Rotation by 2π/n followed by reflection perpendicular to rotation axis Symbol E Cn σ I Sn 5 .

Cn Simple rotation about an axis passing through the molecule by an angle of 360o/n. Identity. 6 O H H 180 o O H H . The identity E operation does nothing.g. The identity E. This operation is called a proper rotation (or simply rotation) and symetry element is symbolized by Cn e. but is important when we consider a set of symmetry elements which form a group. We say water has a C2 rotation axis. E.1. Water – has a two-fold rotation axis (C2 operation) Rotation by 180˚ leaves H2O in identical orientation. No change in the object. Proper rotation. May not seem like an operation at all. ---Needed for mathematical completeness ---Every molecule has this symmetry element 2.

C3 Symmetry element and operations e.g. NH3 has a C3 rotation axis. One can perform two C3 operations 7 .

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- 8 .

Locate the Cn axis in the following molecules. F O C O F B F Cl Cl Pt Cl Cl 2- 9 .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.

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 .

C∞ 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 B F 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 B F 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 .

15 . This axis is the C4 axis. One can perform a C2 operation about the axis.Cl Cl C2 ?? 2Cl Also has this C2 symmetry element? Pt Cl Cl Cl Pt Cl C4 2Cl No.

e. Locate σ planes in the following molecules. water molecule Note that a water molecule can be reflected by two planes. σ. Mirror plane symmetry operation is denoted as σ O H H H O H H O H H O H Exercise.3.g. F O C O F B F Cl Cl Pt Cl Cl 2- 16 . Reflection (Mirror). Reflection of all atoms through a plane.

Answers

F C O F B F Cl

Cl Pt Cl Cl

2-

O

17

Answers

F C O F B F Cl

Cl Pt Cl Cl

2-

O

O

C

O

O

C

O

18

Answers

F C O F
F B F F

Cl B F Cl Pt Cl Cl

2-

O

O

C

O

F B F F B F F

O

C

O

F F B F
19

F

Answers F C O F F B F F Cl B F Cl Pt Cl Cl 2- O Cl Cl Pt Cl Cl 2- O C O 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 O C O F F B F Cl Pt Cl ∞ F .

Type of mirrors F B F σh F F B F F C2 C2 F F F B F σv σh = plane perpendicular to principal axis σv = plane includes the principal axis (σd = a kind of σv plane includes the principal axis. but not the outer atoms) B F C3 F σd O H σv 21 O C O σh C∞ H .

g. F N N F F S F F F The inversion center I could be midway along a bond. e.4.g.g. 22 . i = each point moves through a common central point to a position opposite and equidistant. e. as in SF6. e. Reflection of all atoms through a point. as in N2 molecule. Or may be situated at an atomic center itself. Inversion (Center of Inversion). Each atom has a identical counter-part on the other side of the molecular center.

NO2. O2. Which of these molecules have a center of inversion? H2O. CO2 O H H O O N O O O C O 23 .Question.

NO2. CO2 O H H O O N O O O C O 24 . O2.Question. Which of these molecules have a center of inversion? H2O.

CO2 O H H O O N O O O C O 25 . Which of these molecules have a center of inversion? H2O. NO2.Question. O2.

in either order. Improper rotation Sn.4. Sn = Cn + σh Question. 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. also called Rotation-Reflection The combination. How many S4 rotation axis does a CH4 molecule have? 26 .

C4 H1 H2 C4 C H3 H4 σh H3 H1 H2 C σh H3 C H1 H2 H4 H4 27 .

S4 H H C S4 S4 H H Three 28 .

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.

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 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 L M L L Ru

33

Fa C3 Fb Fc Fa

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

La Lb C3 Lc La

C Ld 3 M Le Ld M Le σh Lb Lc

Fc Fa

Lc La

Le M Ld
34

Lb

L L L M C4 L L L M σh M L 35 L L Ru C5 L L Ru σh Ru L L L L .

Some interesting points: S1 operation is equivalent to the mirror reflection σ S2 is equivalent to a center of inversion i 36 .

Summary of symmetry operations and symmetry elements 37 .

Examples: 38 .

39 .

2σv H E. C3. O H N H H H E. Definition. E. 40 . Point Groups 1. 3σv The complete set of symmetry operations than can be performed on a molecule is called the symmetry group for the molecule. C2. One molecule may have more than one symmetry elements and one can perform various symmetry operations.g.C.

Not accurate! 41 .

4C3. 3C4. 3S4. 4S6. (6+3)C2. 3C2. à Oh 42 . i. 3S4. 6σd à Td E.E. 4C3. 9σ.

43 .

Groups of Low Symmetry E E. Characteristics of Common Point Groups 2. σ E. i 44 .1.2.

2. Cn groups (n = 1. Cnv groups Contain Cn and nσv C2v C3v H C2 σd H O H Cl Examples F Sb F F F σv Br 45 .3.2. 2. …) H H N Contain only one Cn rotational axis B H N H H N C3 2.

Cn groups (n = 1. 2.3. …) H H N Contain only one Cn rotational axis B H N H H N C3 2. Cnv groups Contain Cn and nσv H Cl C2v Examples C2 F F Sb F F Br 46 .2.2.

…) H H N Contain only one Cn rotational axis B H N H H N C3 2.2. 2. Cn groups (n = 1. Cnv groups Contain Cn and nσv H Cl C2v Examples C3v C3 F Sb F F F C2 Br 47 .2.3.

Cnv groups Contain Cn and nσv C2v C3v C3 H C4 Cl C4v Examples C2 F Sb F F F Br 48 .2. …) H H N Contain only one Cn rotational axis B H N H H N C3 2.2.3. 2. Cn groups (n = 1.

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 F 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 F F C4v Cl other 3 σv are not shown 50 .

Cnh groups C n + σh H Cl Cl B H O H O H O C2h H Me C O X Mo R 3P O C Me X O Mo O PR3 O O S O O O O O S O O Re O O Re O S O O S O O 51 .2.4.

Cnh groups C n + σh H Cl Cl B H O H O C2 C2h H O H C2 Me C O X Mo R 3P O C Me X O Mo O PR3 O O S O O O O O S O O Re O O Re O S O O S O O 52 .4.2.

2.4. Cnh groups C n + σh H Cl Cl B H O H O C2 C2h H O C3 H C3h Me C O X Mo R 3P O C Me X O Mo O PR3 O O S O O O O O S O O Re O O Re O S O O S O O 53 .

Cnh groups C n + σh H Cl Cl B H O H O C2 C2h H O C3 H C3h C3 C2 Me C O X Mo R 3P O C Me X O Mo O PR3 O O S O O O C3h O O S O O Re O O Re O S O O S O O 54 .4.2.

4. Cnh groups C n + σh H Cl Cl B H O H O C2 C2h H O C3 H C3h C3 C2 Me C O O X Mo R 3P O C2 O S O O O C3h O O Re O S O C2h Mo X O C Me PR3 O O S O O Re O O S O O 55 .2.

4. Cnh groups C n + σh H Cl Cl B H O H O C2 C2h H O C3 H C3h C3 C2 Me C O O X Mo R 3P O C2 O S O O O C3h O O Re O S O C4h C4 56 C2h Mo X O C Me PR3 O O S O O Re O O S O O .2.

O S O O O O S 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 O O σh S O S O O O Any other symmetry element? 57 .

O S O O O O S 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 O O S O O C4 O S O σh 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 O S O O S4 58 .

Characteristic symmetry elements: Dn groups: Cn + n C2 Dnh group: Cn + n C2 + σh Dnd group: Cn + n C2 + nσv 59 .2. D Groups A Cn principal rotational axis is accompanied by a set of n C2 axes perpendicular to it.5.

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 .

and maybe others too C3 C2 Examples σh Symmetry elements: 61 . perpendicular to the principal axis Cn.b). Dnh groups Characteristic symmetry elements: Cn + nC2 + σh σh: horizontal mirror plane. Also has n σv.

b). Also has n σv. and maybe others too C3 C2 Examples σh S3 Point group: D3h Symmetry elements: σv E. 3σv. σh. S3 62 . Dnh groups Characteristic symmetry elements: Cn + nC2 + σh σh: horizontal mirror plane. C3. 3C2(┴). perpendicular to the principal axis Cn.

XeF4 F F Xe F F Symmetry elements: 63 .

C4. + ? 64 .XeF4 F F Xe F Point group: D4h F Symmetry elements: E. 4σv. σh. 4C2(┴).

4σv.XeF4 F F Xe F Point group: D4h F Symmetry elements: E. σh. i 65 . C4. S4. 4C2(┴).

a square planar geometry C 6H 6 BF3 66 .How about the following species? dual relationship ? [PtCl4]2.

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 .

a square planar geometry C 6H 6 BF3 69 .How about the following species? D3h D6h dual relationship D5h ? [PtCl4]2.

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 .

a square planar geometry C 6H 6 BF3 D6h D5h D3h D3h 71 .How about the following species? D3h D6h dual relationship D4h D5h ? [PtCl4]2.

72 .

c) Dnd group: Characteristic symmetry elements: Cn + nC2 + σv Do not have σh mirror plane Examples: R3W≡WR3 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 + σv Do not have σh mirror plane Examples: R R3W≡WR3 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 .

3C2(┴).c) Dnd group: Characteristic symmetry elements: Cn + nC2 + σv Do not have σh mirror plane Examples: C3 R R3W≡WR3 Point group: D3d R R W W R R R R W R R W R R C2 R R R σv W W R R R R S6 R W R R symmetry elements: E. C3. 3σv. I. S6 R R R i R W W R R 75 R R W R .

Fe Fe Fe Point group: symmetry elements: 76 .

I. 5C2(┴). C5. S10 Fe 77 .C5 σv Point group: D5d Fe Fe C2 Fe S10 i Fe symmetry elements: E. 5σv.

C 2 (┴ ) 78 .

g.Dnd groups Additional examples square antiprism Steggered ethane e. triagular antiprism H H H H C C C H H H H allene 79 .

g.Dnd groups Additional examples Steggered ethane e. triagular antiprism (D3d) σv C2 C2 C3 80 .

g. triagular antiprism (D3d) σv C3 C2 σv C2 C2 D3d C3 81 .Dnd groups Additional examples Steggered ethane e.

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 σv H Point group: D2d C2 H H H H C2 H H H H 83 σv .

Point group: 84 .

Point group: D4d C4 B' C' D' A' C2 A B C σv D 85 .

2.6. Sn ≡ Cnh. Thus n can only be even Me H H Me XB NR BX NR BX N R 86 N RN H Me Me H B X . Sn groups (n = even only because one gets Cnh when n = odd S1 = Cs S2 = Ci When n = odd.

C4 H Me H Me C4 σh σh Me H H Me Me H H Me H Me H Me H Me H Me H Me H Me Point group: S4 Symmetry elements?: S4 87 .

C4 H Me H Me C4 σh σh Me H H Me Me H H Me H Me H Me H Me H Me H Me H Me Point group: S4 88 .

C4 XB RN XB NR C4 XB BX BX RN NR RN XB BX BX σh NR XB σh RN XB BX NR RN BX NR NR RN Point group: S4 89 .

CH4.7. 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. High symmetry point groups a) Tetrahedral point groups Td point group Characteristic symmetry elements: 4C3 + 3C2 (e.g. 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. CH4. High symmetry point groups a) Tetrahedral point groups Td point group Characteristic symmetry elements: 4C3 + 3C2 (e. SiCl4.7.g.

g. Th point group: T + I (rare) 92 . etc…) C3 Cl Si Cl C3 C2 C2 C2 C3 Cl Cl Any other symmetry elements? S4 S4 S4 6σ In addition there are molecules with Th point group. CH4.7. SiCl4.2. High symmetry point groups a) Tetrahedral point groups Td point group C3 Characteristic symmetry elements: 4C3 + 3C2 (e.

10S6. 4C3. 15C2.b) Octahedral point groups Oh point group: Characteristic symmetry elements 3C4 e. 10C3. 4S6. SF6 Additional symmetry elements E. i. 6C2. 6S10. 9σ C4 Icosahedral point groups Ih point group: Characteristic symmetry elements 6C5 + i C5 Additional symmetry elements: E. 3S4. à Ih 93 .g. 15σ.

Summary •  T group: 4C3 •  O group: 3C4 •  I group: 6C5 94 .

a list of symmetry elements could be made and then compare them with list characteristic of each point group. C3. C2. e. (b) NH3 possesses following symmetry elements: E. To identify a molecules point group.g. 3σv) corresponds to the group C3v. Identification of point groups. The set of elements (E. 2σv. To what point groups do H2O and NH3 belong? O H H H N H H (a) H2O possesses the following symmetry elements: E. 3σv. The set of elements (E. C3. 95 . 2σv) corresponds to the group C2v.3. C2.

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 .Alternatively. one can use set of rules for assigning the point group – follow a flow chart (see below).

Exercises: Give the point group of following molecules.5-dibromonaphthalene (b) IF7 (d) trans-HClC=CClH (f) P4 97 . (a) Mer-[Fe(CN)3Cl3]3(c) Mo(CN)84(e) Mn2(CO)10 (g) 1.

Oh. Ih)? Highest Cn? Any C2 ⊥ Cn? Any σh? Any σv? 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? High symmetry (Td.

Ih)? No Highest Cn? C2 Any C2 ⊥ Cn? No Any σh? No Any σv? 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 .Answers N C (a) N C Cl Cl Fe Cl 3Low symmetry? No High symmetry (Td. Oh.

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

F F F I F F F F F F

F F I F F
100

F

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 σh? Yes D5h

F
σh

F F F F F F I F F
101

F I

F F
C2

F

F

NC NC NC Mo CN CN CN

Low symmetry? High symmetry (Td, Oh, Ih)? Highest Cn? Any C2 ⊥ Cn? Any σh? Any σd (or σv)?

NC
NC NC NC Mo CN

CN
NC NC NC Mo CN CN CN CN

CN

NC

CN

NC

CN

102

Ih)? No Highest Cn? C4 Any C2 ⊥ Cn? Yes Any σh? No Any σd (or σv)? 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 σv NC D CN NC CN 103 .C4 NC NC NC Mo CN CN CN Low symmetry? No High symmetry (Td. Oh.

(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) P 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 P 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 .

3C4. 9σ. 6C2. 4S6. 4C3.C4 C4 C4 Oh E. i. à Oh Oh 117 . 3S4.

i.C4 C4 C4 Oh Oh Oh E. 6C2. 4C3. à Oh 118 . 9σ. 3S4. 3C4. 4S6.

Ih Ih Ih Oh 119 . The dodecahedron and the icosahedron form a dual pair. its dual is another tetrahedron).Dual polyhedra Every polyhedron has a dual polyhedron with faces and vertices interchanged. The tetrahedron is self-dual (i.e. The cube and the octahedron form a dual pair.

Point group? 120 .

Point group? Td Oh Oh Ih Ih 121 .

Summary: Some typical shapes of point groups 122 .

123 .

124 .D. + C2 F F Xe F F + σ + + The presence of a mirror plane or a C2 axis rules out a dipole in the direction shown. Molecular polarity A polar molecule is a molecule with a permanent electric dipole moment. Applications of symmetry 1. (2) cannot have a permanent dipole perpendicular to any mirror plane. (3) cannot have a permanent dipole perpendicular to any axis of symmetry. - + F - H + Symmetry consideration: a molecule (1) can not have a permanent dipole if it has an inversion center.

z F F C4 F F F F C3 B F x y Xe Cannot have a dipole in the xy plane 125 .

some Cnh. T. Sn groups Exercises: Which of the following molecules are polar? F Fe F F S Cl F F F S F F F 126 . -Molecules belonging to any D. O or I groups cannot have permanent dipole moment.Conclusion Conclusion: Molecules having both a Cn axis and a perpendicular C2 axis or σh cannot have a dipole in any direction. Molecules can not have a permanent dipole if it has an inversion center .

O or I groups cannot have permanent dipole moment. yes C2v. T.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. -Molecules belonging to any D. yes 127 .Conclusion Conclusion: Molecules having both a Cn axis and a perpendicular C2 axis or σh cannot have a dipole in any direction. Molecules can not have a permanent dipole if it has an inversion center .

2. i ) are chiral. Molecular chirality (分子手性) A chiral molecule (手性分子) 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. 128 . Remember. Sn including S1 = σ and S2 = i Conclusion: a molecule lack of Sn (including σ.

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 F (b) S F F F Me H H Me Has σ. not chiral N N (c) N Co N N N N (d) (e) The skew form of H2O2 H Me Me H 130 .

not chiral Has σ.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 Has σ. not chiral N N (c) N Co N N N N (d) (e) The skew form of H2O2 H Me Me H 131 .

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 F (b) S F F F Me H H Me Has σ. not chiral N N (c) N Co N N N N (d) (e) The skew form of H2O2 Νο σ. not chiral Has σ.

not chiral Has σ.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 Has σ. not chiral N N (c) N Co N N N N (d) (e) The skew form of H2O2 Νο σ. I and Sn =>chiral H Me Me Has S4 not chiral H 133 .

not chiral N N (c) N Co N N N N (d) (e) The skew form of H2O2 Νο σ. I and Sn =>chiral H Me Me Has S4 not chiral H Νο σ. I and Sn =>chiral 134 .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 Has σ. not chiral Has σ.

3. Symmetries of Orbitals Diatomic species Other labels σ2p* π2p* π2p σ2p σ2s* Based on symmetry in relation to rotation. σ2s O2 and F2 135 .

Orbital labels for polyatomic species z x O y H O H 6σ H 5σ 4σ 2pz 2py 2px 3σ 2σ 1σ H z x O y H O H H 2b2 1b1 2pz 2py 2px 2a1 1b2 1a1 136 3a1 H 2s 2s .

which can be assigned by referring to character table.y MO of BH3 z 5σ 4σ x 2e' 2a1' 2py 2px 2pz a2" e' a1' 2s 1a1' 1a2" 1e' 2py 2px 2pz 3σ 2σ 2s 1σ The more elaborated labels are based on the behavior of orbitals under all operations. 137 .

change sign. H C2 O O H H H χ(C2) = -1 +1 -1 0 no change. move to a new place. C2 O O H H H χ(C2) = 1 H C2 O H O H H H χ(C2) = 0 138 .Character. χ Character: a number “indicating” (relating) how an object is affected by a symmetry operation.

C2. Consider pz in C2v Under C2v. 2σv z E χ(E) = +1 C2(z) y χ (C2(z)) = +1 x σv(xz) σv(yz) O H H χ (σv(xz)) = +1 χ (σv(xz)) = +1 139 . we have E.Orbital Symmetry.

Consider px in C2v z E + x σv(xz) y + C2(z) χ(E) = +1 + χ(C2(z)) + σv(yz) + = -1 χ(σv(yz)) = -1 χ(σv(xz)) = +1 140 .Orbital Symmetry.

Orbital Symmetry. Consider px in C2v z E x + y - + C2(z) χ(E) = +1 + χ(C2(z)) = -1 + χ(σ(yz)) = +1 σv(yz) σv(xz) + - χ(σv(xz)) = -1 141 .

(dyz) σxz (dyz) = .(py) σxz (py) = .(dxz) σxz (dxz) = (dxz) σyz (dxz) = .(px) C2 (py) = .(dxz) C2 (dyz) = .(dyz) σyz (dyz) = (dyz) χ 142 .Summary C2 (px) = .(px) σxz (px) = (px) σyz (px) = .(py) σyz (py) = (py) C2 (pz) = (pz) σxz (pz) = (pz) σyz (pz) = (pz) χ C2 (dxz) = .

(dyz) σyz (dyz) = (dyz) -1 1 -1 -1 -1 1 -1 -1 1 1 1 1 143 .(dxz) C2 (dyz) = .(px) σxz (px) = (px) σyz (px) = .(dxz) σxz (dxz) = (dxz) σyz (dxz) = .(py) σyz (py) = (py) C2 (pz) = (pz) σxz (pz) = (pz) σyz (pz) = (pz) χ -1 1 -1 χ C2 (dxz) = .(py) σxz (py) = .Summary C2 (px) = .(dyz) σxz (dyz) = .(px) C2 (py) = .

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 .

y.pz =>x.xz.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.z dxy.dxz.dyz => xy.yz dx2-y2=>x2-y2 dz2 => z2. 2z2-x2-y2 146 . py.

C2 (py) = .g.(py) σyz (py) = (py) C2 ( σxz ( σyz ( )=-( )=-( )=( ) ) ) 147 . e.Molecular orbitals may have the same symetry properties as atomic orbitals.(py) σxz (py) = .

b2. 148 .

More complicated cases H B H H H C3 H B y x C3 x H y H H H B H 149 H B H H B H H H C3 H B H .

y): 0 0 1 E(z): [1] 150 .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.

Character (χ) and matrix x' = [1]x x' = [-1]x χ=1 χ = -1 b c e f h i x y z x' y' z' a d g χ = a+ e+ i 151 .

y): 0 0 1 χ(C3) = -1 χ(C3) = 2 C3(z):[1] χ(C3) = 1 E(z): [1] χ(C3) = 1 152 .C3 (x.y): -1/2 3/2 3/2 -1/2 1 E (x.

Labels for symmetry species 153 .

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

155 .

156 .

Real examples A A σg z y πu πg σu 157 .

H 2O z x O y H O H H 2b2 z y x 3a1 H 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 y H O 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' .

H 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 M L L L p L s M L L d 165 .

Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6 L L M L L symmetry labels for AOs? p L s L M L L d 166 .Exercise.

Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6 L L M L L symmetry labels for AOs? t2 a1 t2 p L s L M L L d e symmetry labels for MOs? 167 .Exercise.

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6 L L M L L 3t2 symmetry labels for AOs? t2 a1 t2 p s L M L L L 2a1 2t2 d 1e 1t2 168 e symmetry labels for MOs? 1a1 .

Exercise. Give symmetry labels of molecular orbitals of Td ML4 and Oh ML6 L L M L L 3t2 symmetry labels for AOs? t2 a1 t2 p s L M L L L 2a1 2t2 d 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 d 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 d 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? .

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

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