10-May-23

CHE4114 – Advanced Inorganic

Chemistry

Assessment : Semester-end examination

3 hour theory paper
All compulsory six questions

Molecular symmetry and Group theory

CHE 4114
Atkins - Physical Chemistry

Ogden – Introduction to Molecular Symmetry (Oxford

Chemistry Primer)
Cotton – Chemical Applications of Group Theory

Davidson – Group Theory for Chemists

Kettle – Symmetry and Structure

Shriver, Atkins and Langford – Inorganic Chemistry

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Alan Vincent – Molecular Symmetry and Group Theory

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What do symmetry and shapes have to do

with chemistry?
Remember that the way waves are allowed to travel through 2D
space depends on the energy of the waves and the shapes of
the plane

The same phenomena happens in 3D space, thus the shape

of molecules dictates the electronic and other properties of
molecules

Symmetry Operation: Moves an object into a new orientation

that is indistinguishable from its original appearance

Symmetry Element: point line or plane with respect to which a

symmetry operation is carried out
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1. Identity Symbol: E
This means do nothing. It represents the lowest
order of symmetry. All molecules posses the identity
symmetry element.

2. Proper rotation axis Symbol: Cn , n = 2, 3, 4, 5,

An axis about which the molecule may be rotated
2πm/n radians. The values of m are 1, 2,. ,n. A two-
fold rotation axis means rotation by π radians, or 180
. A three-fold axis means rotation by 120 , etc. A
molecule may have more than one order of axis; that
axis with the largest value of n (highest order) is
called the principal rotation axis.

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3. Mirror planes Symbol: σh, σv, σd

σh - horizontal mirror plane is a plane of reflection
normal to the principle rotation axis.
σv - vertical mirror plane is a plane of reflection
containing the principle rotation axis.
σd - dihedral mirror plane is a plane of reflection
containing the principle rotation axis which also
bisects two adjacent C2 axes perpendicular to the
principle rotation axis

4. Center of symmetry : i
Also called an inversion, it means simply that: invert
the position of all the atoms with respect to the
center of symmetry of the molecule. In coordinate
language, this means converting x, y, z to -x, -y, -z. 5

The Improper Rotation Operation (Sn)

• The improper rotation operation Sn is also known as
the rotation‐reflection operation and is a compound
operation.
• Rotation‐reflection consists of a proper rotation
followed by reflection in a plane
perpendicular to the axis of rotation.

• n refers to the improper rotation by 2π / n = 360° / n.

• Sn exists if the movements Cn followed by σh (or vice
versa) bring the object to an equivalent position.
• If both Cn and σh exist, then Sn must exist.
e.g., S4 collinear with C4 in planar MX4.
• Neither Cn nor σh need exist for Sn to exist.
e.g., S4 collinear with C2 in tetrahedral MX4 6

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Some Vocabulary
in 3D space there are three types of mirrors
sh = perpendicular to principle axis Cn (highest n)
sv = contains entire principle axis Cn (highest n)
sd = same as sv but contains fewer poins (atoms)

sh = bisects the 2 sd ‘s contain C4 axis and

2 sv ‘s contain C4 axis and three only one Pt atom
Principle (C4 ) axis atoms each
Contains all five atoms (bisecting Cl’s)
(Pt and both Cl’s)

Improper Rotations, Sn
Sn = rotate by 360o/n then reflect into plane
perpendicular to rotation axis ( = Cn*sh)
**A molecule with an Sn axis is not chiral**
example: S4 axis
Top View (2D)
1 2 3
key o S S S
o Out of plane 4 x 4 4
x
x In-plane o
4
E=S 4

Perspective
View (3D)
An S4 axis demarcates the points of a tetrahedron
S1 axis is a mirror plane
S2 axis= inversion center = i
rotate 180o reflect ⊥ to rotation axis
converts (x,y,z) to (-x, -y, -z)
C2 sH

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Special Symmetries
Low symmetry

C1 No symmetry elements other than

identity
Ci Only inversion View down C-C bond

Cs
Only one mirror

High symmetry
K Spherical
Infinite # of mirrors and rotation
axes and C∞’s
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High symmetry
D∞h Linear, Symmetric C2
One C∞, one sh C∞ F F
sv’s
Infinite sv’s, C2’s C2
C∞ sh

C∞v Linear, Asymmetric C∞ C∞

One C∞
Infinite sv’s,
NO sh or C2’s H F

Td Tetrahedral (24 symmetry operations)

But no inversion center!
C3 S4
Rotations:

C2

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Oh Octahedral (48 symmetry operations) (cube or

octahedron) View down C3 and S6
showing sd’s

sh
sd
C4*i = S4 (x3)
Proper rotation axes (only one of
each shown)
C3*i= S6 (x4)
( an inversion center is located
where all cross) C2*i= s (x6)
Ih Icosahedral (120 symmetry operations)
(rare) Examples: C60, (B12H12)2- Six C5
Ten C3
( an Fifteen C2 is located
inversion center
where all cross)
C5*i = S10 (x6)
C3*i= S6 (x10)
C2*i= s (x15) 11

Point Groups
a set of symmetry elements operating on a system in which at
least one point is not translated under any operation

Special Group? no Special Group

start High symmetry? low symmetry?
T, Th, Td, O, Oh, I, Ih C1 Ci, Cs
Multiple high-order axes no
C∞v, D∞h
Linear
Only S2n?
Dnh S4, S6, S8…
sh no
yes Find highest Cn
sd D - group
No s Any ┴ Cn’s?
Dnd no
Dn C - group
No s sv sh
Cn Cnv Cnh
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Point Groups and Properties

Dipole Moments
Only molecules with point groups:
C1  Cn, Cs, and Cnv have dipole moments
trans-[PtBr2I2]2- cis-[PtBr2I2]2-

Point Group: D2h Point Group: C2v

Polar? No Polar? Yes
fac-[WBr3I3] mer-[WBr3I3]

Point Group: C3v Point Group: C2v

Polar? Yes Polar? Yes
Geometric isomers:
Two or more molecules or ions with same empirical formula but
different spatial arrangement of bonded atoms 13

Point Groups and Properties

Chirality
Only molecules with point groups:
C1, C2  Cn, D2  Dn are chiral
Chiral molecules cannot have an Sn axis:
S1 = s and S2 = i:

C2

Point Group: C2 Chiral? Yes Polar? Yes

Optical isomers: Chiral compound and its non-
superimposable mirror image
Place one ring in the back, see
how other ring is connected from
top position to front:
Top left front = L Top right front = D
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Foundations of Group Theory

Group: complete set of symmetry elements inter-related by
certain mathematical rules
Four shared properties of groups:
[1] Each group contains and identity element that commutes all other
members and leaves them unchanged
A·E = E·A = A

Multiplication in group theory is different than arithmetic

In group theory perform symmetry element on right first
“A·E” translated means do E followed by A
Example: s·C 13 s
C 13 s
Do this 1st
s 1
s C 3
NOT this 1st
You might end up somewhere you are
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not supposed to go

Four Shared Properties of Groups, Cont’d.

[2] Each symmetry operation has an inverse that when combined with
the original symmetry element yields the identity

A·(A)-1 = E thus, if (A)-1 = B then A·B=E

Some symmetry elements are their own inverse
E·E = E
do nothing followed by do nothing = do nothing
C2·C2 = E
180o rotation followed by a 180o rotation = 360o rotation = do nothing

In general for rotations, inverse of C m is C (n-m)

n n
(4-1)
(C1)-1 = C 4 =C3
4 4

C 3 ·C 1 = E C 14
4 4 3
C 4
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Four Shared Properties of Groups, Cont’d.

[3] The product of any two symmetry operations gives rise to another
or the same member of a group (closure requirement)

C 3 C 14
2 1 3 4
C 4
·C 4
= C 4
2
C 4
Example 2, in C3v point group:
sv”
sv ·C 13 =? C 13 sv ·C 13 = sv’
sv ’
sv
[4] The Associative Law holds: A(BC) = (AB)C
perform product1 in parentheses first
Example in C3v C 13 (svsv’) = (C 3 sv)sv’
sv”
C 1 sv”
3
sv ’
2 2
sv C 3
= C 3
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Developing members of the C3 Point group

In order to form a group the above four conditions MUST be met

[1] Each group contains and identity element, E

[3] if C31 is a member, then products must be
members
E·E = E C31·C31 = C32
E·C31 = C31 New member!
Does this new member generate any more members?
Found inverse C32·C31 = E NO new
members! C 3
2·C 2 = C 1
3 3 members
Property
[2]
Does the Associative Law hold? Property [4]
(build a multiplication table to evaluate this)

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Group Multiplication Tables

Does the association law hold?
First operation
E C 13 C 23
2nd operation
C3
E E C 13 C 23
1
C 3 C 13 C 23 E
C 23 C 23 E C 13
1 1 1
C 3
(C 1
3
· C 23 ) = (C 3
·C 3
) C 23
3 2
C = E C 3
3
1 1
C 3 = C 3

Yes, associative law holds,

all four criteria are met, this is a complete group

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Construction of Character Tables

There are several methods for converting group multiplication tables
into numbers useful for later manipulations
Method (1) Brute Force Substitution
-Substitute numbers for each character ci(R) ,
& see if arithmetically and group mult. valid
C2v E C2 sv sv’
E E C2 sv sv’
C2 C2 E sv’ sv
sv sv sv’ E C2
sv’ sv’ sv C2 E

Gi,’s = irreducible representations: non-trivial solutions that cannot be

simplified
If each character were zero, this would be a trivial case

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Construction of Character Tables

Checking the Projection Operator Method
Try G2: c(E) = c(sv) = 1 & c(C2) = c(sv’) = -1
1= -1= 1= -1= 1= -1= 1= -1=
C2v E C2 sv sv’ C2v E C2 sv sv’
1= E E C2 sv sv’ 1= E +1 -1 +1 -1
-1= C2 C2 E sv’ sv math -1= C2 -1 +1 -1 +1
1= sv sv sv’ E C2 1= sv +1 -1 +1 -1
-1= sv’ sv’ sv C2 E -1= sv’ -1 +1 -1 +1
Check that the original group/# assignments hold:
C2·sv = sv’ Mathematically correct
Original assignment c(sv’) = -1
(-1)·(1) = (-1) NOW holds! Try others…
Works easily for simple point groups like this
- difficult for multidimensional representations.
Example: almost impossible to do for C3v
unless use f-orbitals
for C4v you would need g- orbitals and math
tricks… 21

Construction of Character Tables

Method (2) Projection Operator Method
See how nodal properties of various orbitals change under various
operations.
(a) Assign right handed axes
(b) Usually highest Cn = z-axis
(c) If lobes stay same = +1
if lobes change sign = -1
C2v E C2(z) sv(xz) sv(yz)
z

x y +1 +1 +1 +1 Same = G1

different = G2
+1 -1 +1 -1
Another
+1 -1 -1 +1 different = G3
x the last
different = G4
y +1 +1 -1 -1
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Properties of groups
1. Total # of symmetry operations = order of the
group (h)

2. Symmetry operations are arranged in classes

C2v point groups, 4 classes.

3. # of irreducible representation = class ( rows = columns)

4. The sum of the squares of the dimensions ( under E) = h

5. Sum of squares of characters multiplied by the # of operations = h

6. Irreducible representations are orthogonal to each other.

7. A totally symmetric representation is included

In all groups, with character of 1 for all operations. 23

Construction of Character Tables

Practice on a real easy example
C2 E C2 # classes = 2
E E C2 Each element is in a class with itself
C2 C2 E 2 irreducible rep’s

C2 E C2 Totally C2 E C2
G1 symmetric G1 1 1
G2 Rep. exists G2

C2 E C2 dimensionality
orthogonality G1 1 1 S li = h
2

S g(R)[ci(R)][cj(R)] = 0 G2 1 l12 + l22 = 2

12 + l22 = 2
g(E)[c1(E)]*[c2(E)] + g(C2)[c1(C2)]*[c2(C2)] = 0
l22 = 1
1*1*1 +1*1*[c2(C2)] = 0 l2 = ±1
1 + [c2(C2)] = 0 C2 E C2 but c(E) is always
[c2(C2)] = -1 G1 1 1 positive
G2 1 -1 l2 = +1
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Construction of Character Tables

Example of C3v
# classes:

# members = 3
(sv1 , sv2, and sv3)
# members = 2 (C31 and
C32)
C3v E 2C3 3sv
G1
G2 Three classes
G3 = 3 irred. reps

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Construction of Character Tables

Example of C3v

C3v E 2C3 3sv 3 classes=3 irred. reps

G1 1 1 1 (totally symmetric rep. exists) G1 =
G2 1 +1 +1 +1
dimensionality
G3 2
S li2 = h
Hopefully it is obvious that one of l12 + l22 + l32 = 1+2+3
these must be 1 while the other is 2 1 2 + l 22 + l 32 = 6
l22 + l32 = 5
The bigger l #’s are lower in the table
orthogonality G1*G2: finding characters for G2
g(E)*[c1(E)]*[c2(E)]+g(C3)*[c1(C3)]*[c2(C3)]+g(sv)*[c1(sv)]*[c2(sv)]=0
1*1*1 +2*1*[c2(C3)] + 3*1*[c2(sv)] = 0
C3v E 2C3 3sv 1 +2*[c2(C3)] + 3*[c2(sv)] = 0
G1 1 1 1 c2(C3) must be 1 and c2(sv)
G2 1 1 -1 is -1
G3 2 26

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Construction of Character Tables

Example of C3v
C3v E 2C3 3sv
G1 1 1 1 finding characters for G3
G2 1 1 -1
G3 2 (a) G1*G3= 0
g(E)*[c1(E)]*[c3(E)]+g(C3)*[c1(C3)]*[c3(C3)]+g(sv)*[c1(sv)]*[c3(sv)]=0
1*1*2 +2*1*[c3(C3)] + 3*1*[c3(sv)] = 0
Multiple possibilities:
(-1, 0) or (2, -2) or
2[c3(C3)] + 3[c3(sv)] = -2
(0, -2/3), etc… (b) G2*G3= 0
g(E)*[c2(E)]*[c3(E)]+g(C3)*[c2(C3)]*[c3(C3)]+g(sv)*[c2(sv)]*[c3(sv)]=0
1*1*2 +2*1*[c3(C3)] + 3*(-1)*[c3(sv)] = 0
2[c3(C3)] - 3[c3(sv)] = -2
2[c3(C3)] + 3[c3(sv)] = -2 C3v E 2C3 3sv
2[c3(C3)] - 3[c3(sv)] = -2 G1 1 1 1
4[c3(C3)] = -4 G2 1 1 -1
[c3(C3)] = -1  [c3(sv)] = 0 G3 2 -1 0
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convert Gn’s to Mulliken Symbols

D4 E 2C4 C 2 2C2 2C2’

4
A1 G1 1 1 1 1 1 z
A2 G2 1 1 1 -1 -1 xy
B2 G3 1 -1 1 -1 1 x2-y2 xyz
B1 G4 1 -1 1 1 -1 (x,y)
E G5 2 0 -2 0 0
Mulliken
c(E) Symbol Subscripts:
1 A Symmetric (+1) to 1 = symm (+1) for
highest C C2 ┴ to Cn of D group
1 B asymmetric (-1)n
or sv of C group
2 E 2 = asymm (-1) for
C2 ┴ to Cn of D group
3 T
or sv of C group
4 G g = gerade
symm (+1) to inversion
5 H u = ungerade
Superscripts: = asymm (-1) to i
Single prime ‘ = symm (+1) to sh
Double prime “ = asymm (-1) to sh 28

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Character Tables
C2v E C2 sv(xz) sv’(yz)
A1 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x Ry
B2 1 -1 -1 1 y Rx
Gxyz 3 -1 1 1

Add together characters of

irreducible reps spanning x, y & z
(A1+B1+B2)
= translational elements
this is a REDUCIBLE representation

Can be decomposed to simpler irreducible representations

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Reducing a Reducible Representation

a
C2v E C2 sv(xz) sv’(yz)
A1 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 b 1 -1 1 -1 x Ry
B2 1 -1 -1 1 y Rx Character of
Gxyz 3 -1 1 1 symmetry operation
c
# times irred. Rep. is “R” in reducible
found in reducible representation
rep. a b
ai = (1/h) SR (gR)[ci(R)][cj(R)]
c
Order = sum of Coefficient of Character of
coefficients in front of symmetry symmetry oper. “R” in
symmetry operations operation irred. rep
For C2v: h = 1+1+1+1 = 4
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