Lecture 34: Symmetry Elements The material in this lecture covers the following in Atkins.

15 Molecular Symmetry The symmetry elements of objects 15.1 Operations and symmetry elements 15.2 Symmetry classification of molecules (a) The groups C 1,Ci, and Cs (b) The groups Cn,Cnv, and Cnh (c) The groups Dn,Dnh, and Dnd Lecture on-line Symmetry Elements (PowerPoint) Symmetry Elements (PDF) Handout for this lecture

Symmetry elements The systematic discussion of symmetry is called Some objects are more symmetrical than others

Any rotation of sphere around axis through center brings sphere over into itself

Some of the symmetry elements of a cube. The twofold, threefold, and fourfold axes are labelled with the conventional symbols. Only some rotations of sphere brings cube into itself

Symmetry elements

(a) An NH3 molecule has a threefold (C3) axis

(b) an H2O molecule has a twofold (C2) axis. Both have other symmetry elements too.

NH3 has more rotation symmetry than H 2O

Symmetry elements An action that leaves an object the same after it has been carried out is called a :

Symmetry operations are :

For each symmetry operation there is a

symmetry element

Which is

with respect to which the operation is performed

Operators and Symmetry elements The classification of objects according to symmetry elements corrsponding to operations that leave at least one common point unchanged gives rise to the :

There are five kinds of symmetry operations and corresponding symmetry elements 1. The identity E Consists of doing nothing

Only element for CFClBrI

Cl I Br

Operators and Symmetry elements

-1 C3 and C3 C6

(b) an H2O molecule has a twofold (C2) axis.

The principle rotation axis is the axis of the higest fold

C5

C6 ; C3 ; C2 -1 -1 and C6 ; C3

Operators and Symmetry elements

The H2O molecule has two mirror planes. They are both vertical (that is contain the vertical axis) and as so are denoted v and v'

C6

Operators and Symmetry elements

C2 C2

C2

Benzene has one mirror plane perpendicular to the principle C6 - axis (h )

Dihedral mirror planes ( d ) bisect the C2 axis perpendicular to the principle axis

Operators and Symmetry elements

A regular octahedron has a centre of inversion (i).

Operators and Symmetry elements

(a). A CH4 molecule has a fourfold improper rotation axis (S4): the molecule is indistinguishable after a 90 rotation followed by a reflection across the horizontal plane, but neither operation alone is a symmetry operation.
C4

Operators and Symmetry elements

(b) The staggered form of ethane has an S6 axis composed of a 60 rotation followed by a reflection.

The Symmetry Classification of Molecules The Schoenflies system Hermann Mauguin

The Symmetry Classification of Molecules

The groups C1 , Ci , Cs

C1 , Ci , Cs

F Cl I
HO

A molecule belongs to C1 if it has only the identitity E

Br
COOH H

A molecule belongs to Ci if it has only the identitity E and i

OH

HOOC

Meso-tartaric acid

A molecule belongs to Cs if it has only the identity and a mirror plane

Quinoline

The Symmetry Classification of Molecules

The groups Cn , Cnv , and C nh A molecule belongs to Cn if it has a Cn axis and the identitity E only

Cn

C2

C3

C4

C5

C6

C2
O H O H

H2O2

The Symmetry Classification of Molecules

The groups Cn , Cnv , and C nh

Cnv

A molecule belongs to Cnv if it has a Cn axis and n vertical mirror planes

cone
C5 v

C2 v

C3 v

C4 v

C6 v

Cv

CO Heteronuclear diatomics are Cv

C3 v
H2O C 2v

NH3

The Symmetry Classification of Molecules

The groups Cn , Cnv , and C nh

Cnh

A molecule belongs to Cnh if it has a Cn axis and a horizontal mirror plane

C2h
Cl C C H

C3h
H

C4h

C5h

C6h
H O

B O O H B(OH)3

Cl

Trans CHCl=CHCl

The Symmetry Classification of Molecules

The groups Cn , Cnv , and C nh
C2

Cnh

The presence of a twofold axis and a horizontal mirror plane jointly imply the presence of a centre of inversion in the molecule.

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh A molecule belongs to D n if it has a Cn axis and n two fold axes (C2 ) perpendicular to Cn .
N

Dn

N Pt N N

D3

A molecule with n twofold rotation axes perpendicular to an n-fold rotation axis belongs to the group Dn.

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh

Dn

D2

D3

D4

D5

D6

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh A molecule belongs to Dnh if it has a Cn axis and n two fold axes (C2 ) perpendicular to Cn as well as a horizontal mirror plane.

Dnh

A molecule with a Mirror plane perpendicular to a Cn axis, and with n twofold axes in the plane, belongs to the group Dnh.

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh A molecule belongs to D nh if it has a Cn axis and n two fold axes (C2 ) perpendicular to Cn as well as a horizontal mirror plane.

Dnh
C2

H C

C2
C H

C4
H

D2h

C4

D2h

D3h
Cl h Au Cl Cl Cl

C2 C'2 C2

C2

D4h

D4h

D5h

D6h

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh A molecule belongs to Dnh if it has a Cn axis and n two fold axes (C2 ) perpendicular to Cn as well as a horizontal mirror plane.
F

Dnh

E , C3 , 3C2 , h

E , C6 , 3C2 , 3C'2 , h

The Symmetry Classification of Molecules

The groups Dn , Dnv , and D nh

Dnh

C3
F

h C2
F

C2

C2
F

D3h

The Symmetry Classification of Molecules The groups Dn , Dnv , and D nh A molecule belongs to Dnd if in addition to the elements of Dn it posesses n dihedral mirror planes

Dnd

D2d

D3d

D4d

D5d

D6 d

C2 C2
C C C

C2

D2d

What you must learn from this lecture

1. Given a molecule, you should be able to identify the different symmetry elements (Cn,v,h,d,i,Sn, etc. ) 2. Having identified the symmetry elements of a molecule, you should be able to establish the point group to which the molecule belong