Molecular Symmetry

Symmetry Elements and

Symmetry Operations
• Identity
• Proper axis of rotation
• Mirror planes
• Center of symmetry
• Improper axis of rotation
 Symmetry Elements and
Symmetry Operations
• Identity => E
 Symmetry Elements and
Symmetry Operations
• Proper axis of rotation => Cn
– where n = 2, 180o rotation
– n = 3, 120o rotation
– n = 4, 90o rotation
– n = 6, 60o rotation
– n = , (1/ )o rotation
• principal axis of rotation, Cn
2-Fold Axis of Rotation
3-Fold Axis of Rotation
Rotations for a Trigonal Planar Molecule
 Symmetry Elements and
Symmetry Operations
Mirror planes =>
h => mirror plane perpendicular to a
principal axis of rotation
v => mirror plane containing principal
axis of rotation
d => mirror plane bisects dihedral angle made
by the principal axis of rotation and two
adjacent C2 axes perpendicular to principal
rotation axis
 Mirrors
v v
Cl Cl
h
I d
d
Cl Cl
Rotations and Mirrors in a Bent
Molecule
Benzene Ring
 Symmetry Elements and
Symmetry Operations
• Center of symmetry => i
Center of Inversion
Inversion vs. C2
 Symmetry Elements and
Symmetry Operations
• Improper axis of rotation => Sn
– rotation about n axis followed by inversion
through center of symmetry
Improper Rotation in a Tetrahedral
Molecule
S1 and S2 Improper Rotations
 Successive C3 Rotations on
Trigonal Pyramidal Molecule
Linear Molecules
 Selection of
Point Group from Shape
• first determine shape using Lewis Structure
and VSEPR Theory
• next use models to determine which
symmetry operations are present
• then use the flow chart Figure 3.9, Pg. 81
text to determine the point group
Decision Tree
 Selection of
Point Group from Shape
1.determine the highest axis of rotation
2.check for other non-coincident axis of
rotation
3.check for mirror planes
H2O and NH3
Geometric Shapes
 Orbital Symmetry, pz C2v
z E + X(E) = +1
- +
+ C2(z)
x
- + - X(C2(z)) = +1
y v(xz)
- X(v(xz)) = +1
v(yz) +

- X(v(xz)) = +1
 Orbital Symmetry, py C2v
- X(E) = +1
z
+
E
- C2(z) +
x - X(C2(z)) = -1
+
v(xz)
y +
- X(v(xz)) = -1
v(yz)
-
+ X(v(xz)) = +1
 Orbital Symmetry, px C2v
z
- + X(E) = +1
E
x C2(z)
- + + -
X(C2(z)) = -1
y v(xz)
- +
X((xz)) = +1
v(yz)

+ - X(v(xz)) = -1
 Water, C2v Point Group
Translational motion in y
z

y o o
H H H H

x v(xz)

“asymmetric” => -1
 Water, C2v Point Group
Translational motion in y
z

o
y H H
x o
H H
v(yz)
“symmetric” => +1
 Water, C2v Point Group
Translational motion in y
z

y C2(z)
x

O
H H
“asymmetric” = - 1
 Water, C2v Point Group
Translational motion in y

Representation:
E C2(z) v(xz) v(yz)
3 +1 -1 -1 +1
 Water, C2v Point Group
Rotation about z axis
z

O
H Hb
a
 - movement out of plane towards observer
 - movement out of plane away from observer
a,b - labeling to distinguish hydrogens before and
after symmetry operations
 Water, C2v Point Group
Rotation about z axis
z

O E O
H Hb H Hb
a a
+1
 Water, C2v Point Group
Rotation about z axis
z

O C2z O
H Hb H Ha
a b
+1
 Water, C2v Point Group
Rotation about z axis
z

O v(xz) O
H Hb H Ha 
a b

x -1
 Water, C2v Point Group
Rotation about z axis
z

O v(yz) O
H Hb H Hb
a a
-1
 Water, C2v Point Group
Rotation about z axis

Representation
E C2(z) v(xz) v(yz)
4 +1 +1 -1 -1
 Water, C2v Point Group
Representations:
Rotation
E C2(z) v(xz) v(yz)
4 +1 +1 -1 -1
 Water, C2v Point Group
Representation:
Translation
E C2(z) v(xz) v(yz)
1 +1 +1 +1 +1 Tz
2 +1 -1 +1 -1 Tx
3 +1 -1 -1 +1 Ty
 Water, C2v Point Group
Representation:
Rotation
E C2(z) v(xz) v(yz)
4 +1 +1 -1 -1 Rz
5 +1 -1 +1 -1 Ry
6 +1 -1 -1 +1 Rx
 Water, C2v Point Group
Character Table
E C2(z) v(xz) v(yz)
A1 +1 +1 +1 +1 Tz 1
A2 +1 +1 -1 -1 Rz 4
B1 +1 -1 +1 -1 Ry, Tx 2 , 5
B2 +1 -1 -1 +1 Rx,Ty 3, 6
Vibrational Modes in CO2

For linear molecules: 3N - 5 IR fundamentals

Vibrational Modes in SO2

For non-linear molecules: 3N - 6 IR fundamentals

 Vibration Modes for SO3

For non-linear molecules: 3N - 6 IR fundamentals

Vibrational Modes for CH4

For non-linear molecules: 3N - 6 IR fundamentals

Vibrational Modes for [PtCl4]-2

For non-linear molecules: 3N - 6 IR fundamentals

Enantiomer Pairs
Enantiomer Pairs
Polarimeter