CHEM 411: Symmetry & Structure

Unit I - Symmetry Groups

(part-1 by Dr.RP)

Text Books to be referred:

• Chemical Applications of Group Theory (Third Edition), F. A. Cotton
• Symmetry and Spectroscopy of molecules, K. Veerareddy
• Molecular Symmetry and Group Theory: R. L. Carter
• Symmetry and Spectroscopy, D. C. Harris and M. D. Bertolucci

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Shapes - Symmetry

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 Symmetry
• Cf. Greek word “synmetron”
• Mutual relation of parts of something
• Line
• Widely used by designers, painters and singers • Plane
• The poet Keats wrote • Point

– “Beauty is Truth and Truth is Beauty”

• Prof. Herman Weyl defined the term Symmetry:
– “After some operations of a thing has exactly the same
configurations then it is said to be symmetrical”
• There are three geometrical entities such as a point, line and
plane about which the object is symmetrical. It is named as
Symmetry Element.

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 Symmetry Point Group Notations
• Schönflies notation – Spectroscopy
– named after German Mathematician Arthur Moritz Schönflies
– used to represent the point group and describe the symmetry of a
molecule

• Hermann-Maunguin notation – Crystallography

– able to describe the space group of the crystal symmetry

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 SU-DO-KU WORDOKU
4 W E
7 2 I A
1 R K
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 Group and its properties
• Group
– It is a collection of elements that are interrelated according
to a certain rules. Any mathematical system that obeys the
following four rules is called a group.
• Axioms (basic rule) of a Group
 Closure

 Associativity

 Identity

 Inverse

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 Properties of a Group
• Closure rule
– The product of any two elements and the square of each element must be an element in the group.
Perhaps we could say it is combination instead of product.
– For example, if a and b are in the group then a • b is also in the group.
• AB=C and BA=C then A and B are commutative – leads to Abelian -----> C2v
• AB=C and BA=D then A and B are not-commutative -----> C3v
• A2=E and B2=E

• Associative rule
– All the symmetry elements must obey the associative law of multiplication
– If a, b and c are in the group then (a • b) • c = a • (b • c)
• A(BC) = (AB)C; A(BC)D = (AB)(CD)

• Identity rule
– There should be at least one element in the group must commute with all others and leave them
unchanged.
– There is an element e of the group such that for any element a of the group a • e = e • a = a
• AE=EA=A

• Inverse rule
– Each element has a reciprocal, which is also an element of the same group
– For any element a of the group there is an element a-1 such that a • a-1 = e and a-1 • a = e
• RS = SR = E, where R is the reciprocal of S
• E is its own reciprocal
• Inverse of a proper axis, Cnm = Cnn-m -----> C52 = C53

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 TOOL  Group Multiplication Table
• Order of the group h is nothing but the number of elements present in the
group
• This consists of h rows and h columns that means it has h2 elements and it
is square.
• The entries are results from the product (combination) of the elements
which head that column and that row.
– (Column element) * (Row element)
• It is rearrangement theorem: Each row and each column in the GMT lists
each of the group elements once and only once. No two rows may be
identical nor any two columns. Thus each row and each column is a
rearranged list of the group elements.
• Groups of order 1, 2, 3 etc. forms different level of abstraction groups
– G3 forms only one abstract group and it leads to CYCLIC group
– G4 forms two abstract groups (G4(1) , G4(2))
• Order of the group is ODD then it forms only one abstract group.
• If the group is symmetry w.r.to diagonal and all elements obey
commutative then it is said to be Abelian 8
 Group of Integers: Addition / Multiplication

• Addition group: Consider the set, Z4={0, 1, 2,

3}, together with addition modulo 4.

• Multiplication group of integers: Consider the

subset Z10* = {1, 3, 7, 9} of Z10. It is easy to check
that the subset, together with addition modulo
10, forms a group of 4 elements.

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 Types of Group
• Cyclic group
• Abelian and Non-abelian group
• Dihedral group
• Homomorphic/ Isomorphic group
• Permutation group
• Abstract group
• Continuous group
• Infinite group
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 Simple Examples
Example 1: C1 C1 e Realizations:

e e • {e} = { 1 }

Example 2: C2 Realizations:
e a
• {e,a} = { 1, –1}
a e
• Reflection group: C = { E, σ }
Cn = Rotation of angle 2π/n
• Rotation group: C2 = { E, C2 }

Realizations:
Example 3: C3 e a b
• Rotation group: C3 = { E, C3 , C3–1 }
a b e
• Cyclic group: C3 = { e, a, a2 ; a3=e }
b e a
• { 1, e i 2π/3, e i 4π/3 }
• Cyclic permutation of 3 objects
{ (123), (231), (312) }
Cyclic group : Cn = { e, a, a2, a3, … an-1 ; an = e }
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 Classes
• Sorting out the elements of a point group
• The main classes of point groups are C, D, S, T, O, and I.
• Two elements A & B in a group form a class if they are conjugate to each other. The related by
similarity transformation: X-1 A X = B, then A and B are conjugate.
• Self Conjugation – Every element is conjugate with itself
• Mutual Conjugation – If A is conjugate with B, then B is conjugate with A
• Associative Conjugation – If A is conjugate with B and C, then B and C are conjugate with each
other
• A complete set of elements that are conjugate to one another is called a class of the group.
• No element of the group occurs in more than one class
• The order of all classes must be integral factors of the order of the group.
• C3v  E C31 C32 σv σv ’ σv ”
self mutual associative
h=6  g=1 + g=2 + g=3
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 Subgroups
• Any subset element which form a group and satisfies
the four basic rules is called as subgroup
• If H is a subgroup of G then it is HG
• Order of subgroup (s) < order of the group (g), i.e.,
g/s is a natural number.
• Example: Possible subgroups of C2V point group
G: C2v  {E, C2(z), (xz), (yz)}; Order of the group = 4
H: {E}  C1 Order of the subgroup = 1
{E, C2}  C2 s=2
{E, }  Cs s=2

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 Group Homomorphism/ Isomorphism:
• When we compare the additive table (Z4,+) and the multiplicative
group (Z10,*), then they “have a great deal in common”.

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Common group table

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 Isomorphism
• Isomorphism = iso (equal) + morph (shape)

• Isomorphic groups possess the same multiplication table and same

algebraic structure, but differ in symmetry operations and selection
rules.

• There is one-to-one correspondence (bijection = one-to-one and onto)

between the elements of the two isomorphic groups.

• On the other hand, it is a homomorphism with one-to-one and onto .

• Collections of isomorphic groups are said to belong to the same

abstract group.

• i.e., Two abstract groups of order 4, one made up from S4 and C4, and
the other made up from C2h, C2v and D2.

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 Level of Abstraction - Isomorphic Groups
Order Icosa-
Sn Cn Cnh Cnv Dn Dnd Dnh Cubic
h hedral
1 C1
2 S2 C2 C1h
3 C3
4 S4 C4 C2h C2v D2
5 C5
6 S6 C6 C3h C3v D3
7 C7
8 S8 C8 C4h C4v D4 D2d D2h
9 C9
10 S10 C10 C5h C5v D5
12 S12 C6h C6v D6 D3d D3h T
14 S14 C7h C7v D7
16 S16 C8h C8v D8 D4d D4h
18 S18 C9h C9v D9
20 S20 C10h C10v D10 D5d D5h
O, Td
24 D6d D6h
Th
48 Oh
60 I
120 http://www.staff.ncl.ac.uk/j.p.goss/symmetry/index.html Ih 17
 Permutation Groups
The order of any subgroup g of a group of order h must be a divisor of h. h/g = k
The simplest non-Abelian group is of order 6. Not symmetry w.r.to diagonal
{ e, a, b = a–1, c = c–1, d = d–1, f = f–1 }
Aliases: Dihedral group D3, C3v, or
Permutation group S3 e C3 C 32 1 2 3
C3 C 32 e 3 1 2
e a b c d f
C 32 e C3 2 3 1
a b e f c d
1 2 3 e C3 C32
b e a d f c
2 3 1 C 32 e C3
c d f e a b
3 1 2 C3 C 32 e
d f c b e a
f c d a b e

Symmetries of an equilateral triangle:

C3v = { E, C3, C32, σ1, σ2, σ3 }
D3 = { E, C3, C32, C2', C2'', C2''' } 18
 (…) = cyclic permutations
S3 = { e, (123), (132), (23), (13), (12) }

S4 = Group of permutations on a set with 4 elements  Symmetric Groups

= Permutations of {1,2,3,4} has 4! = 24 No. of possible permutations
(1 2 3 4) (1 2 3 4) (1 2 3 4) n!
(1 3 4 2) * (4 3 2 1) = (2 4 3 1)
i.e., 1 maps to 4 and 4 maps to 2, the combination result is 1 maps to 2
(bijection)

e (123) (132) (23) (13) (12) e (12) (23) (31) (123) (321)
(12) e (123) (321) (23) (31)
(123) (132) e (12) (23) (13) (23) (321) e (123) (31) (12)
(132) e (123) (13) (12) (23) (31) (123) (321) e (12) (23)
(123) (31) (12) (23) (321) e
(23) (13) (12) e (123) (132) (321) (23) (31) (12) e (123)
(13) (12) (23) (132) e (123)
Tung's notation
(12) (23) (13) (123) (132) e

S4 = { e, (12)(34), (13)(24), (14)(23)}  D2 = {E, C2, C2’, C2”}

S4 = {e, (1234),(13)(24),(1432)}  C4 = {E, C41, C42, C43}
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 Definitions to remember
 “After some operations of a thing has exactly the same configurations then
it is said to be Symmetrical“ – Prof. Herman Weyl
 Group is a collection of elements that are interrelated according to a
certain rules
 Point group is a set of symmetry operations forming a mathematical group,
for which at least one point remains fixed under all operations of the
group. It is a method of classifying the shapes of molecules according to
their symmetry elements.
 Symmetry operation is an operation performed on an object which leaves
it in a configuration that is indistinguishable from, and superimposable on,
the original configuration. To take the object into an equivalent
configuration.
 Symmetry element is a geometrical entity such as a point, a line, or a plane
with respect to these a symmetry operation may be carried out.
 All symmetry elements are associated with their symmetry operations.
 Order of the group is the total number of symmetry operations in that
group. 20
Symmetry Elements

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 Symmetry Elements
• The proper axis of symmetry is an imaginary line through a compound.
Rotation of the compound by an integral fraction of a circle around this axis
(1/2, 1/3, etc.) brings the compound to superposition on itself. An axis of
symmetry is represented by Cn, where n is the integral fraction. All shapes
have at least a C1 axis (the identity axis).
• The improper axis of symmetry is also an imaginary line through a
compound. Rotation of the compound by an integral fraction of a circle
around this axis (1/2, 1/4, etc.) followed by reflection through a plane
perpendicular to this axis brings the compound to superposition on itself.
An improper axis of symmetry is represented by Sn, where n is the integral
fraction (n must be even or 1).
• The plane of symmetry is a plane through a compound that relates its
identical halves. A plane of symmetry is represented by σ and is the same as
an S1 axis.
• The inversion center (or point of symmetry) is an imaginary point in a
compound. Reflection of the compound through this point brings the
compound to superposition on itself. An inversion center is represented by i
and is the same as an S2 axis (C2 followed by h). 22
 Specifying Molecular Symmetry

Symbol Symmetry Element Symmetry Operation

Cn Axis of symmetry n-fold rotations about the axis

σ Plane of symmetry Reflection in the plane

i Center of symmetry / Reflection of all atoms through the

Center of inversion molecular center

Sn Improper axis of n-fold repetitions of the sequence:

symmetry rotation followed by reflection in a
plane r to the principle rotation axis

E Identity Einheit , unity, no change / doing

nothing

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Rotational Axes:
 Angle of rotation,  = 360/n
 Principle axis of rotation - Cn
 Secondary rotational axes - nC2

Planes of Symmetry:
 Vertical plane - σv contains the principle axis
 Horizontal plane - σh perpendicular to the p.a.
 Dihedral plane - σd contains p.a. and bisects the angle
between two C2 axes perpedicular to the p.a.

1
Improper rotation:
3 2
 Principle axis rotation followed by a reflection plane
6 4
perpendicular to the p.a. (horizontal plane)
 Snm = Cnm . σhm 5
S6
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Some Important Relations:

Symmetry Symmetry Repetition Inverse n m

operation Element value (n)
Cnn E even/ odd Snn-m Even Even

σn E even Snn-m Even Odd

σ odd
In E even Cnn-m Odd Even
i odd
Sn2n-m Odd Odd
Snn E even
σ odd

The symbol Cnm represents a rotation by 2/n carried out successively m times.

Snm represents the operations Cn and σ have been carried out for m times.

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Some Important Relations:

C4 = C 4 1 , C 4 2 , C 4 3 , C 4 4
 E, 2C4, C2
S4 = S 4 1 , S 4 2 , S 4 3 , S 4 4

S41 = C41 h1

S42 = C42 h2 = C2
Example S43 = C43 h3 = C43 h
S4 4 = E
 E, 2S4, C2

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 Illustrative Examples

http://symmetry.otterbein.edu/gallery/index.html
http://chemwiki.ucdavis.edu/Theoretical_Chemistry/Symmetry/Common_Point_Groups
_for_Molecules/Symmetry_Point_Groups

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 Geometries (with lone pair)
AXE method
A – Central atom
X – number of sigma bonds
E – number of lone pairs

Key Points
 Linear: a simple triatomic molecule of the type AX2; its two bonding orbitals
are 180° apart
 Trigonal planar: triangular and in one plane, with bond angles of 120°
 Tetrahedral: four bonds on one central atom with bond angles of 109.5°
 Trigonal bipyramidal: five atoms around the central atom; three in a plane
with bond angles of 120° and two on opposite ends of the molecule
 Octahedral: six atoms around the central atom, all with bond angles of 90°
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Five basic geometries using VSEPR theory

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Geometries based on atomic position
(without lone pairs)

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 Rotation about n-fold axis of symmetry

Axis of rotation = 360/n

BF3: Planar – D3h

NH3: Nonplanar – C3v

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 Reflection through a plane of symmetry

C2v

C v Dh
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Example: XeF4

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Reflection through a centre of symmetry - inversion

Improper Rotation:

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 Higher-order Symmetry Groups

Tetrahedron Octahedron Icosahedron

4 faces 8 faces 20 faces

Td (24) Oh (48) Ih (120)

P4 W(CO)6 [B12H12]2- 35
Procedure to find out the
molecular point group

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Flow-chart 1:

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Flow-chart 2:

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Symmetry Type Symmetry Group Point Group Major elements Order (h)
Nonaxial Symmetries Asymmetry C1 E alone 1
Inversion group Ci E, i 2
Reflection group Cs E, σ 2
(Cyclic) Axial Symmetries Cyclic groups Cn C nm n
Reflection groups Cnh C n + σh 2n
Pyramidal groups Cnv Cn + nσv 2n
Improper rotation Sn (n=even) C n + σh n
Dihedral Symmetries Dihedral groups Dn Cn + nC2 2n
Prismatic groups Dnh Cn+nC2 + σh 4n
Antiprismatic groups Dnd (n >= 2) Cn+nC2 + nσd 4n
Polyhedral Symmetries Tetrahedral groups T, Td, Th multi-C3 12, 24,24
Octahedral groups O, Oh multi-C4 24, 48
Icosahedral groups I, Ih multi-C5 60, 120
Spherical groups Kh C 
Linear groups (Infinite) Cv (C+ σv), 
Dh (C+C2+i+σh)
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Homework: Get the examples for all the above symmetry types !!!
Examples

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CHFClBr: C1 H2O2: C2 CH2Cl2F2: Ci

CH2ClF: Csh HCN: Cv H2: Dh

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H2O: C2v NH3: C3v SF5Cl: C4v

Dibenzpentalene B(OH)3: C3h

C2h
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Allene (C3H4): D2d Ethane (C2H6): D3d

S8: D4d Staggered Fe(C5H5)2: D5d

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Ethylene (C2H4): D2h Eclipsed (C2H6): D3h

PdCl42-: D4h Eclipsed Fe(C5H5)2: C6H6: D6h

D5h
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 ML6

Methane (CH4): Td SF6: Oh

Buckminster Fullerene
C60Br24: Th C60: Ih 45
Matrix Representation of Symmetry Operations

R
Initial Final

Final Vector = (Transformation matrix, (R)) * Initial vector

Method 1: using Cartesian coordinates (x, y, z)

Method 2: Numbered atoms in a molecule

Identity by Unit Matrix (E):

Inversion Matrix (i):

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Reflections: w.r.to Plane

Proper Rotation: w.r.to Axis

The matrix for a rotation about axis z by an arbitrary angle Θ is derived easily if we
imagine two two-dimensional coordinate planes with identical origin but an angular
difference of Θ between the axes.

Cn(z):
n=2,3,4,..

Improper Rotation: w.r.to Axis Sn(z):

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For n=2 with different axes 

Method 1: Method 2:

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 Group Representations
The matrix representatives obey the same multiplication table as the operators
Example: Water molecule which has C2v point group, the operations are E, C2(z), xz, yz

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Ammonia molecule (C3v): Group representations

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