Chapter 4

Molecular Symmetry

Dr. S. M. Condren
Dr. S. M. Condren
 Symmetry Elements and
Symmetry Operations
• Identity
• Proper axis of rotation
• Mirror planes
• Center of symmetry
• Improper axis of rotation

Dr. S. M. Condren
 Symmetry Elements and
Symmetry Operations
• Identity => E

Dr. S. M. Condren
 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

Dr. S. M. Condren
2-Fold Axis of Rotation

Dr. S. M. Condren
3-Fold Axis of Rotation

Dr. S. M. Condren
Rotations for a Trigonal Planar Molecule

Dr. S. M. Condren
 Symmetry Elements and
Symmetry Operations
Mirror planes =>
sh => mirror plane perpendicular to a
principal axis of rotation
sv => mirror plane containing principal
axis of rotation
sd => mirror plane bisects dihedral angle made
by the principal axis of rotation and two
adjacent C2 axes perpendicular to principal
rotation axis

Dr. S. M. Condren
 Mirrors
sv sv
Cl Cl
sh
I sd
sd
Cl Cl

Dr. S. M. Condren
Rotations and Mirrors in a Bent
Molecule

Dr. S. M. Condren
Benzene Ring

Dr. S. M. Condren
 Symmetry Elements and
Symmetry Operations
• Center of symmetry => i

Dr. S. M. Condren
Center of Inversion

Dr. S. M. Condren
Inversion vs. C2

Dr. S. M. Condren
 Symmetry Elements and
Symmetry Operations
• Improper axis of rotation => Sn
– rotation about n axis followed by inversion
through center of symmetry or reflection.
Improper Rotation in a Tetrahedral
Molecule
 Improper Rotation
The staggered
conformation of
ethane has an S6 axis
that goes through
both carbon atoms.
 Improper Rotation

Note that an S1
axis doesn’t exist; it
is same as a mirror
plane.
 Improper Rotation

Likewise, an S2
axis is a center of
inversion.
S1 and S2 Improper Rotations

Dr. S. M. Condren
 Successive C3 Rotations on
Trigonal Pyramidal Molecule

Dr. S. M. Condren
Linear Molecules

Dr. S. M. Condren
 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

Dr. S. M. Condren
Dr. S. M. Condren
Decision Tree

Dr. S. M. Condren
 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

Dr. S. M. Condren
H2O and NH3

Dr. S. M. Condren
Dr. S. M. Condren
Dr. S. M. Condren
Geometric Shapes

Dr. S. M. Condren
 Orbital Symmetry, pz C2v
z E + X(E) = +1
- +
+ C2(z)
x
- + - X(C2(z)) = +1
y sv(xz)
- X(sv(xz)) = +1
sv(yz) +

- X(sv(xz)) = +1

Dr. S. M. Condren
 Orbital Symmetry, py C2v
- X(E) = +1
z
+
E
- C2(z) +
x - X(C2(z)) = -1
+
sv(xz)
y +
- X(sv(xz)) = -1
sv(yz)
-
+ X(sv(xz)) = +1

Dr. S. M. Condren
 Orbital Symmetry, px C2v
z
- + X(E) = +1
E
C2(z)
- + x + -
X(C2(z)) = -1
y sv(xz)
- +
X(s(xz)) = +1
sv(yz)

+ - X(sv(xz)) = -1

Dr. S. M. Condren
 Water, C2v Point Group
Translational motion in y
z

y o o
H H H H

x sv(xz)

“asymmetric” => -1

Dr. S. M. Condren
 Water, C2v Point Group
Translational motion in y
z

o
y H H
x o
H H
sv(yz)
“symmetric” => +1

Dr. S. M. Condren
 Water, C2v Point Group
Translational motion in y
z

y C2(z)
x

O
H H
“asymmetric” = - 1
Dr. S. M. Condren
 Water, C2v Point Group
Translational motion in y

Representation:
E C2(z) sv(xz) sv(yz)
G3 +1 -1 -1 +1

Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis
z

O
rH Hbs
a
r - movement out of plane towards observer
s - movement out of plane away from observer
a,b - labeling to distinguish hydrogens before and
after symmetry operations
Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis
z

O E O
rH Hbs rH Hbs
a a
+1

Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis
z

O C2z O
rH Hbs rH Has
a b
+1

Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis
z

O sv(xz) O
rH Hbs sH Har
a b

x -1

Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis
z

O sv(yz) O
rH Hbs sH Hbr
a a
-1

Dr. S. M. Condren
 Water, C2v Point Group
Rotation about z axis

Representation
E C2(z) sv(xz) sv(yz)
G4 +1 +1 -1 -1

Dr. S. M. Condren
 Water, C2v Point Group
Representations:
Rotation
E C2(z) sv(xz) sv(yz)
G4 +1 +1 -1 -1

Dr. S. M. Condren
 Water, C2v Point Group
Representation:
Translation
E C2(z) sv(xz) sv(yz)
G1 +1 +1 +1 +1 Tz
G2 +1 -1 +1 -1 Tx
G3 +1 -1 -1 +1 Ty

Dr. S. M. Condren
 Water, C2v Point Group
Representation:
Rotation
E C2(z) sv(xz) sv(yz)
G4 +1 +1 -1 -1 Rz
G5 +1 -1 +1 -1 Ry
G6 +1 -1 -1 +1 Rx

Dr. S. M. Condren
 Water, C2v Point Group
Character Table
E C2(z) sv(xz) sv(yz)
A1 +1 +1 +1 +1 Tz G1
A2 +1 +1 -1 -1 Rz G4
B1 +1 -1 +1 -1 Ry, Tx G2 , G5
B2 +1 -1 -1 +1 Rx,Ty G3 , G6

Dr. S. M. Condren
Dr. S. M. Condren
Vibrational Modes in CO2

For linear molecules: 3N - 5 IR fundamentals

Dr. S. M. Condren
Vibrational Modes in SO2

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

Dr. S. M. Condren
 Vibration Modes for SO3

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

Dr. S. M. Condren
Vibrational Modes for CH4

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

Dr. S. M. Condren
Vibrational Modes for [PtCl4]-2

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

Dr. S. M. Condren
Enantiomer Pairs

Dr. S. M. Condren
Enantiomer Pairs

Dr. S. M. Condren
Polarimeter

Dr. S. M. Condren