Lecture 35: Symmetry Groups The material in this lecture covers the following in Atkins. 15 Molecular Symmetry 15.

2 Symmetry classification of molecules (d) The groups Sn (e) The cubic groups (f) The full rotation group 15.3 Some immediate consequences of symmetry (a) Polarity (b)Chirality Lecture on-line Symmetry Groups (PowerPoint) Symmetry Groups (PDF) Handout for this lecture

The Symmetry Classification of Molecules

Sn

Posesses the inproper rotation axis Sn

S2 same as Ci
COOH HO H

H HOOC

OH

S4
3 S4 : S4 , C2 , S4 2 S4 = C2
S4

S6
5 C 3 , C 2 , i , S6 , S6 3

S8
3 S 2 ; C4 ; S 8 , C 2 3 S 8 5 , C4 , S 7 8

Meso-tartaric acid

The Symmetry Classification of Molecules

Cubic groups

These groups have more than one principle axis C3 C 2 S4 C3 Td d

C3

C3

The Symmetry Classification of Molecules

Cubic groups
Oh

C3 S6
F F S F F

F F

C4 C2 S4

The Symmetry Classification of Molecules

Cubic groups

I
C5
The relation of an icosahedron to a cube. The buckminsterfullerene molecule (15) is related to this object by cutting off each apex to form a regular pentagon.

C3

The Symmetry Classification of Molecules

Cubic groups
T

C2

Shapes corresponding to the point groups (a) T. The presence of the windmill-like structures reduces the symmetry of the object from Td.

C3

The Symmetry Classification of Molecules C3

Cubic groups

O
Shapes corresponding to the point groups (b) O. The presence of the windmill-like structures reduces the symmetry of the object from Oh.

C4 C2

The Symmetry Classification of Molecules

Cubic groups
Th

The shape of an object belonging to the group Th.

The Symmetry Classification of Molecules

C O N N

Molecu le
N

Linear ?

Dh
N N

i?

N
C O

Cv

Two or more cn n>2 ?

i?

In

C5

Oh

Td

Select C n with highest n; than, are the nC 2 perpendicular to Cn ?

Y

The Symmetry Classification of Molecules

F Cl I Br
N

Quinoline
COOH HO H

n ?
H OH

HOOC

Meso-tartaric acid

s
N

Quinoline
COOH HO H

i
H HOOC OH

i?

N
Cl

1
F I Br

Meso-tartaric acid

The Symmetry Classification of Molecules

n ?

Y N

Dnh

h ?
s

N Y
N

Dnd

n d ?

Dn
i

i?

Select C n with highest n; than, are the nC 2 perpendicular to Cn ?

The Symmetry Classification of Molecules

n ?

N
H O

C2
O O H

H O

B O H B(OH)3

Cnh

h ?

H2O2

Cn
S4

N
S2n ?

Cnv
C3 v NH3

n v ?

S2n

The Symmetry Classification of Molecules

(a) A molecule with a Cn axis cannot have a dipole perpendicular to the axis, (but (b) it may have one parallel to the axis.

Dipole moments

r ss s = (r )rdr

The arrows represent local contributions to the overall electric dipole, such as may arise from bonds between pairs of neighbouring atoms with different electronegativities.

The Symmetry Classification of Molecules

Dipole moments
COOH HO H

H O

F
H OH

H O
HOOC

B O H B(OH)3

Cl I

Br

0
C2
O H O H

Meso-tartaric acid =0 inversion

Quinoline 0 in plane
Cl

=0 h symmetry
H C C H Cl

H2O2
0 along C2

0 along C3

0 along C2

Trans CHCl=CHCl =0 inversion

The Symmetry Classification of Molecules

Chirality
Can only contain a Cn axis
COOH H

A chiral molecule is a molecule that can not be superimposed on its mirror image
C2

C2

H2N

Not chiral
O H O H H O O
COOH

H
CH3 H2N H

HOOH

Mirror image

chiral

Groups and group multiplications

A mathematical group, G = {G,}, consists of a set of elements G = {E, A,B,C,D,....} A binary relation, called group multiplication is defined such That:

(a) The product of any two elements A and B in the group is another element in the group, i.e., we write AB G.

(b) If A, B, C are any three elements in the group then (AB)C = A(BC). Therefore, group multiplication is associative, and frequently, we omit the brackets.

Groups and group multiplications

(c) There is a unique element E in G such that EA=AE=A, for every element A in G. The element E is called the identity element.

(d) For every element A in G, there is a unique element X in G , such that XA = AX = E. The element X is referred to as the inverse of A and is denoted A-1.

Groups and group multiplications

z

HA HB
y x

HA HB C
Cl B

HB HA C2 C Cl B Cl B Cl A

C ClA
HA HB C ClA Cl B (yz) C ClA

ClA
HB HA

Cl B

HA HB C ClA Cl B (xz) Cl B

HA H B C Cl A

Groups and group multiplications

z

HA HB

HA HB
y x

(yz)(xz) C ClA Cl B

H B HA C

C ClA
HA HB (xz)C2 C

C2 Cl B

Cl A

Cl B
H B HA C Cl A Cl B

ClA

Cl B

(yz)

HA HB (yz)C2 C ClA Cl B

H A HB C

(xz)

Cl B

Cl A

Groups and group multiplications

C2v E C2 (xz) (yz)

E E C2 (xz) (yz)

C2 C2 E (yz) (xz)

(xz) (xz) (yz) E C2

(yz) (yz) (xz) C2 E

1. In each row and each column, each operation appears once and only once (2) We can identify smaller groups within the larger one. For example, {E,C2} is a group. There are two others; what are they? (3) In this particular table, we observe that the group product is commutative. This is not necessarily true for other groups.

This table contains all the information about the group and its structure. The name of this molecular point group is C2v. There are some observations to make about this table.

The Symmetry Classification of orbitals

Diatomics Parity of orbitals

The parity of an orbital is even (g) if its wavefunction is unchanged under inversion in the centre of symmetry of the molecule, but odd (u) if the wavefunction changes sign. Heteronuclear diatomic molecules do not have a centre of inversion, so for them the g,u classification is irrelevant.

The Symmetry Classification of orbitals

Diatomics Parity of orbitals

The parity of an orbital is even (g) if its wavefunction is unchanged under inversion in the centre of symmetry of the molecule, but odd (u) if the wavefunction changes sign. Heteronuclear diatomic molecules do not have a centre of inversion, so for them the g,u classification is irrelevant.

Reflection index

Diatomics

=1
g
=1

The Symmetry Classification of orbitals

The in a term symbol refers to the symmetry of an orbital when it is reflected in a plane containing the two nuclei.

=1
u

g
= 1

The Symmetry Classification of orbitals

A rotation through 180 about the internuclear axis leaves the sign of a orbital unchanged

but the sign of a orbital is changed.

In the language introduced in the next lecture, the characters of the C2 rotation are +1 and -1 for the and orbitals, respectively.

What you should learn from this lecture 1. For a given molecule be able to identify all the symmetry elements 2. From the list of elements be able to identify the point group Using a provided flow chart similar to that given by Atkins

The Symmetry Classification of Molecules

Dipole moments

r The components x OH1 r and x are equal in

OH2

y
r OH1
+

r OH2
+ H

magnetude but opposite in sign as they are related by a rotation around C2

Water has local dipoles along each bond Or r x r OH2 x OH1r O r y y

OH1
H

C2
O H H

OH2
H

C2

x OH1

r =

x OH2

They can be decomposed into x and y components

Only dipole along principle axis possible