Group theory: ACC 31131

Monsoon Semester 2016-2017

Dr. Sumanta Kumar Padhi

Assistant Professor
Department of Applied Chemistry
Indian School of Mines Dhanbad, 826 004, INDIA
• Symmetry
Relationship between parts of an object with respect to size, 
shape and position.

e.g In nature: 
• Symmetry Element: 
 A symmetry element is a geometric entity e.g. a point, a line or a
plane.
 Symmetry element is a point, line or plane about which a
symmetry operation is performed

• Symmetry Operator:
 A symmetry operator performs and action on a three
dimensional object.
 A symmetry operation moves an object into an indistinguishable
orientation .
 Symmetry operators are like other mathematical operators (x, ,
+, log, cos, sin, etc..)
• There are five types of symmetry operators:
Operator Symbol
Identity E
Rotation C
Mirror Plane 
Inversion i
Improper rotation S
• There are five symmetry elements, which will be defined relative 
to point with coordinate (x1,y1,z1): 

• Identity, E 
E(x1 ,y1 ,z1) = (x1 ,y1 ,z1)
This operator does nothing and is required for a completeness.  It
is equivalent to multiplying “1” or adding “0” in algebra.
• Proper rotation axis, Cn (where θ= 2/n)
Convention is a clockwise rotation of the point.
The symmetry element is called axis of symmetry and denoted
by Cn.
C2(z) (x1 ,y1 ,z1) = (‐x1 ,‐y1 ,z1) ; in this case θ = 180°
Many molecules have more than one symmetry axis. The axis 
with higher “n” values is called principal axis.

n = (2/θ)θ→0; n = ∞; Cn = C∞
Water has a 2-fold axis of rotation. When rotated by
180o, the hydrogen atoms trade places, but the
molecule will look exactly the same.

Ammonia has a C3 axis. Note that there are two

operations associated with the C3 axis. Rotation by 120o
in a clockwise or a counterclockwise direction provide
two different orientations of the molecule.
 principal axis
(highest value of Cn) Rotational axes of BF3

C3 C3 C2 C2

three-fold axis three-fold axis two-fold axis two-fold axis

viewed from viewed from viewed from viewed from
above the side the side above
Note: there are 3 C2 axes
Rotational axes of BF3
• Plane of Reflection ()
xz (x1 ,y1 ,z1) = (x1 ,‐y1 ,z1) 

H1

H2
yz
xz
• Plane of Symmetry is of three types
1. Vertical plane (v) 
2. Horizontal plane (h)
3. Dihedral plane (d) 
• Horizontal plane (h)
If a plane is  to the principal axis then it is called h
• Vertical plane (v)
If the plane is along the principal axis then it is called vertical plane (v) 
• Dihedral plane (d) 
If the plane bisects the angle subtended between two similar consecutive
C2‐axis
Mirror planes (σ) of BF3:
Mirror planes can contain the principal axis (σv) or be at
right angles to it (σh). BF3 has one σh and three σv planes:
(v = vertical, h = horizontal)

σv σh
mirror plane C3 mirror plane
principal axis C3
principal axis

σv mirror plane σh mirror plane

contains the C3 axis is at right angles to the C3 axis
Rotational axes and mirror planes of benzene C2
C6 C2
principal axis

C6 σh C2 C2

σv σv

C6
C6 principal axis
principal axis
• Inversion (i)
All the points in the molecule are reflected through a single point. 
The point is the symmetry element for inversion.  The position of the (x,y,z) 
coordinate changes to thecorresponding –ve coordinate (‐x,‐y,‐z).
center of symmetry center of symmetry
• Improper  rotation (Sn)
Rotation by 2/n followed by reflection,  to the rotation axis. 
Since performing  two times is the same as doing nothing (E), therefore S
can only be performed odd number of times.
• Improper  rotation (Sn)
• Sn (Improper Rotation Operation) = rotation about 360/n axis followed by reflection 
through a plane perpendicular to axis of rotation
a. Methane has 3 S4 operations (90 degree rotation, then reflection)
b. 2 Sn operations = Cn/2 (S24 = C2)
c. nSn = E, S2 = i, S1 = s 
d. Snowflake has S2, S3, S6 axes
Types of matrices:

 Rectangular Matrix
 Column Matrix
 Row matrix
 Zero null matrix
 Square matrix
 Diagonal Matrix
 Scalar Matrix
 Unit or Identity Matrix
Equal Matrices:
Direct product of two matrices:
Trace or Character of a matrix
Trace or character of matrix is the sum of the diagonal elements.
It is represented by “”.
E or Identity Matrix:

E(x1 ,y1 ,z1) = (x1 ,y1 ,z1)

 Matrix: xz (x1 ,y1 ,z1) = (x1 ,-y1 ,z1)
Plane of symmetry () Matrix:
 Matrix:
Inversion (i) Matrix:
Inversion (i) Matrix:

Therefore, the inversion (i) matrix is:

Cn Matrix:
x2 = r [cos  cos  + sin  sin ]
x2 = r [sin  cos  - cos  sin ]
Sn Matrix:
Sn Matrix:
The following matrices form a representation of the C2h point group

E C2 xy i

The following matrices form a representation of the C3v point group→

• The symmetry properties of an object (e.g. atoms of a molecule,
set of orbitals, vibrations). The collection of objects is commonly
referred to as a basis set .

 Classify objects of the basis set into symmetry operations .

 Symmetry operations form a group.
 Group mathematically defined and manipulated by group theory.
Definition of a group
Group Multiplication table for C2h:
• E is always in a class by itself. It can be transformed into itself by 
all the elements in the group.
• Inversion element , i, is in class by itself.
• All Cnm axes are in a class.
• Similar C2s are in a class.
• Like Cnm all Snm axes are in a class. If there are two or many such 
types they are placed in as many classes.
• Similar vertical (v) and similar dihedral planes (d) are in a class.
• Horizontal plane (h) is a special plane and is always placed in a 
different  class from other planes.
• In all Abelian point groups each element is in a class by itself i.e., 
the number of symmetry elements or order of the group is equal 
to the number of classes.
Number of Classes = Order of the group (h)
• In non Abelian groups the number of classes  is always less than 
the order of the group.
• No element in the group occurs in more than one class.
• The collection of symmetry elements present in a 
molecule forms a ‘group’, typically called a POINT 
GROUP.

• The symmetry elements can combine only in a 
limited number of ways and these combinations 
are called the POINT GROUP.

WHY IS IT CALLED A “POINT GROUP”??

 Because all the symmetry elements (points, lines, 
and planes) will intersect at a single point. 
• In symmetry, a point group is the collection of symmetry operations that leaves a
molecule unchanged.
• Groups with very high symmetry:
1. Icosahedral, Ih
2. Octahedral, Oh
3. Tetrahedral, Td
• Groups with low symmetry:
1. C1 – molecules with only the E element
2. Cs – molecules with E and a single plane of symmetry (σ).
3. Ci – molecules with only E and a center of inversion, i.
• Groups with an n‐fold axis of rotation:
1. Cn – identity (E) and n‐fold rotation (Cn)
2. Cnv – identity (E), n‐fold rotation (Cn) and n vertical reflections (σv).
3. Cnh – identity (E), n‐fold rotation (Cn) and horizontal reflection plane (σh). 
• Dihedral groups: 
1. Dn – identity (E), n‐fold rotation (Cn) and n two‐fold rotations (C2) perpendicular to Cn
axis (principal axis). (with no mirror planes)
2. Dnh ‐ identity (E), n‐fold rotation (Cn), n two‐fold rotations (C2) perpendicular to Cn
axis and horizontal reflection plane (σh). (with a horizontal mirror plane)
Website for symmetry operations:

http://symmetry.otterbein.edu/gallery/index.html
C1 Point Group:
The simplest point group C1 contains only one trivial symmetry operation, the identity operation E. This is the point group of all asymmetrical 
molecules and molecular conformations. These molecules must be chiral:

Cs Point Group:
This point groups has a mirror plane σ as the only symmetry element. Many (flat) aromatic molecules belong to this group.

1- bromo, 2-chloro ethene

Ci Point Group:
If a molecule possesses only an inversion center i and no other symmetry elements, it belongs to the point group Ci. Examples of this group are 
commonly found with meso‐type structures such as meso‐tartaric acid.
Cn Point Groups:
Molecules in this group have a single n‐fold rotation axis Cn as their symmetry element. These compounds must be chiral, and many of the 
most important ligands used in stereoselective synthesis of organic chemistry belong to the C2 point group.
Cn Point Groups:
Molecules in this group have a single n‐fold rotation axis Cn as their symmetry element. These compounds must be chiral, and many of the 
most important ligands used in stereoselective synthesis of organic chemistry belong to the C2 point group.
Cn Point Groups:
Molecules in this group have a single n‐fold rotation axis Cn as their symmetry element. These compounds must be chiral, and many of the 
most important ligands used in stereoselective synthesis of organic chemistry belong to the C2 point group.
Cn Point Groups:
Molecules in this group have a single n‐fold rotation axis Cn as their symmetry element. These compounds must be chiral, and many of the 
most important ligands used in stereoselective synthesis of organic chemistry belong to the C2 point group.

Cn
O O

H2
1H

C2 C2

C3
P

C3
Cnv Point Groups:
Molecules having a n‐fold rotation axis Cn and n vertical mirror planes σv belong to the Cnv point group. Linear molecules which do not possess 
an inversion center or ahorizontal mirror plane σh belong to the C∞v point group, because all rotations about their axis are symmetry operations (conical 
molecules).
C2v Point Groups:
C2v Point Groups:

B2Br4 has the following staggered structure:

C2v Point Groups of Os complexes:
C2v Point Groups:
C2v Point Groups:

mer-[CoCl3(NH3)3]
C3v Point Groups of Os complexes:
C3v Point Groups of Triflate ion:
C3v Point Groups:
C4v Point Groups:

Nido-[Ge]94- [Mn(CO)5Cl]
C4v Point Groups:

IF5 ClF5

SbF5
XeOF4 Or WOF4
C4v Point Groups:

IOF5 IOF5
C5v Point Groups:

Undecaborate ion Undecaborate ion

C6v Point Groups:

Galium(6-C6Me6)
C6v Point Groups:

IOF6- IOF6-
Cnh Point Groups:
Molecules belonging to the Cnh point group feature a n-fold rotation
axis Cn and a horizontal mirror plane σh.

Trans-1,2-difluorodiazine
Isomers of Trans-[Co(en)2Cl2 :

,-Trans-[Co(en)2Cl2]:
,-Trans-[Co(en)2Cl2]
C2h Point Groups:
,-Trans-[Co(en)2Cl2]

,-Trans-[Co(en)2Cl2]
C2h Point Groups:

C2

C2
C2h Point Groups:

C2
C2h Point Groups:

1,5-dibromonaphthalene 1,5-dibromonaphthalene
C3h Point Groups:

Boric Acid Benzotrifuroxan

C4h Point Groups:

Tetraazidocopper(II)
C6h Point Groups:

Cyclophane
C6h Point Groups:

Hexakis(Me2N)Benzene
Point Groups of cis-Platin and trans-Platin:
Point Groups of cis-and trans-[Co(NH3)4(Cl)2]:
Dn- Point Groups :
A molecule that has a n-fold principal axis and n twofold axes perpendicular to the
principal axis belongs to the Dn point group. All molecules in this point
group must be chiral.
D2- Point Groups : ,-Trans-[Co(en)2Cl2]:
C2h point group

,-Trans-[Co(en)2Cl2]
D2- Point Groups :
D2- Point Groups :

C2 C2

C2

Biphenyl-skew form (0<<90o)

D3- Point Groups :

[Co(Ox)3]3-
Tris(oxalate)Iron(III)
D3- Point Groups :

C2 C2

C3

C2
[Ru(en)3] [Ru(en)3]
D4- Point Groups :

Tetrathiacyclododecane
D5- Point Groups :

[YbI2(THF)5]
D5- Point Groups :

[Ferrocene twisted]
D6- Point Groups :

[Bis(benzene)Chromium]
Dnh- Point Groups :
If, in addition to a n-fold principal axis and n twofold axes perpendicular to it,
a horizontal mirror plane σh is present in a molecular structure, the point group is
described as Dnh. The D∞h point group includes all linear molecules with an center
of inversion, which also implies a horizontal mirror plane σh (cylindrical molecules).
D2h- Point Groups :

[Dinitrogen tetroxide]
D2h- Point Groups :
C2
C2

C2

Diborane
D2h- Point Groups :

[Dinitrogen tetroxide]
D3h- Point Groups : Bicyclo[2,2,2]octane
D3h- Point Groups :

Cyclopropane
D4h- Point Groups :

OsCl2(CO)4
D4h- Point Groups :

[Re2Cl8]2-
D4h- Point Groups :
D4h- Point Groups :
D5h- Point Groups :

Ferrocene-eclipsed
D6h- Point Groups :

Coronene
D6h- Point Groups :

Tropilium cation
D8h- Point Groups :

[Bis(COT)Th]4-:
COT = cyclooctatetraene
Dnd- Point Groups :

The Dnd point groups include the symmetry elements of Dn and n dihedral mirror
planes σd bisecting the angles formed by pairs of C2 axes.
D2d- Point Groups :
D2d- Point Groups :

Tetrabromoneopentane
D3d- Point Groups :

Cyclohexane-chair form
D3d- Point Groups :

Staggered-ethane
D4d- Point Groups :

[Os2Cl8]2-
D5d- Point Groups :

Staggered Ferrocene
Sn- Point Groups :
Molecules which have not been classified by one of the above C or D point groups,
but which possess one rotary-reflection axis Sn only (n must be even and ≥ 4),
belong to the Sn point groups. Molecules of point groups Sn with n > 4 are rare.
S4- Point Groups :

12- Crown-4
S4- Point Groups :

[Co4Cp4] cluster
S4- Point Groups :

[bis(dth)CuI]: dth=2,4-dithiahexane
S4- Point Groups :

Tetrabromopentane
S4- Point Groups :

Tetramethyl-COT
S6- Point Groups :

18-Crown-6
S6- Point Groups :

Bis(9-ane-S3)Copper(II): 9-ane-S3 = 1,4,7-Trithiacyclononane

Td- Point Groups :
The tetrahedral point groups are characterized by the presence of four C3 principal
axes (and three C2 axes). The Td group is the point group of a regular tetrahedron. If,
in addition, a center of inversion is present, the point group is Th (molecules of this
group do not look like tetrahedrons, but retain the rotational symmetry of a
tetrahedron). All objects possessing the rotational symmetry of a tetrahedron, but
no plane of reflection or center of inversion are based on the simpler point group T.
Molecules of this group must be chiral, and examples are very rare.
Oh- Point Groups :
The octahedral point groups O and Oh feature three C4 principal axes (and
four C3 axes as well as multiple C2 axes). A regular octahedron and a cube both
belong to theOh point group. In analogy to the tetrahedral point group T, the
octahedral group O retains the rotational symmetry of an regular octahedron, but
none of its planes of reflection or the center of inversion. Examples of molecules
belonging to the O point group are extremely rare (these molecules must be
chiral!).
Ih- Point Groups :

The icosahedral point groups I and Ih posses six C5 principal axes (amongst
10 C3 and 15 C2 axes). In analogy to the octahedral point
groups O and Oh the I group does contain all rotational symmetry elements, but
no mirror planes or center of inversion. Molecules belonging to this chiral point
groups are extremely rare. Shapes belonging to the more symmetrical Ih point
groups are the dodecahedron and the icosahedron.

Kh- Point Group :

The Kh point group resembles the symmetry of perfect spheres. Obviously, only
atoms but no molecules belong to this point group.
 S8: D4d [Co(Ox)3]3- : D3

SF5Cl: C4v C3H4: D2d C60: Ih CH2ClF:

H2O2: C2
Cs Or C1h

H2: Dh HCN: Cv

Suppose that A is a square matrix. The number  is said to be an eigenvalue of A if
for some non-zero vector x, Ax = x. Any non-zero vector x for which this equation
holds is called an eigenvector for eigenvalue or an eigenvector of A corresponding to
eigenvalue .

• Finding eigenvalues and eigenvectors

To determine whether is an eigenvalue of A, we need to determine whether there

are any non-zero solutions to the matrix equation Ax = x. Note that the matrix
equation Ax = x is not of the standard form, since the right-hand side is not a fixed
vector b, but depends explicitly on x. However, we can rewrite it in standard form.
Note that x = Ix, where I is, as usual, the identity matrix. So, the equation is
equivalent to Ax = Ix, or Ax−Ix = 0, which is equivalent to (A−I)x = 0. Now, a square
linear system Bx = 0 has solutions other than x = 0 precisely when |B| = 0.
Therefore, taking B = A − I, is an eigenvalue if and only if the determinant of the
matrix A − I is zero. This determinant, p() = |A − I|, is known as the characteristic
polynomial of A, since it is a polynomial in the variable . To find the eigenvalues, we
solve the equation |A − I| = 0. Let us illustrate with a very simple 2 × 2 example.