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7/17/2019 Introduction to Group Theory.pdf
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Dr. Sumanta Kumar Padhi
Assistant Professor Department of Applied Chemistry
Indian School of Mines Dhanbad, 826 004, INDIA
ACC 32138
Winter Semester 2013 2314
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• Symmetry
Relationship between parts of an object with respect to size,shape and position.
e.g In nature:
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• Symmetry Element:
A symmetry element is a geometric entity e.g. a point, a line or aplane.
Symmetry element is a point, line or plane about which asymmetry operation is performed
• Symmetry Operator:A symmetry operator performs and action on a three
dimensional object.
A symmetry operation moves an object into an indistinguishableorientation .
Symmetry operators are like other mathematical operators (x, ÷,+, log, cos, sin, etc..)
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• There are five types of symmetry operators:
Operator Symbol
Identity E
Rotation CMirror Plane σ
Inversion i
Improper rotation S
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• 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. Itis equivalent to multiplying “1” or adding “0” in algebra.
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• Proper rotation axis, Cn (where θ= 2π/n)
Convention is a clockwise rotation of the point.The symmetry element is called axis of symmetry and denotedby 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 = (2π/θ)θ→0; n = ∞; Cn = C∞
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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.
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.
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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
C3 C3 C2 C2
principal axis
(highest value of Cn)
.
Rotational axes of BF3
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Rotational axes of BF3
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• Plane of Reflection (σ)σ
xz (x1 ,y1 ,z1) = (x1 ,-y1 ,z1)
σxz
σyz
H1
H2
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• Plane of Symmetry is of three types
1. Vertical plane (σ
v)2. Horizontal plane (σh)
3. Dihedral plane (σd)
• Horizontal plane (σh)
If a plane is ⊥ to the principal axis then it is called σh
• Vertical plane (σv)If the plane is along the principal axis then it is called vertical plane (σv)
• Dihedral plane (σd)
If the plane bisects the angle subtended between two similar consecutive
C2-axis
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Mirror planes can contain the principal axis (σ v) or be atright angles to it (σ h). BF3 has one σ h and three σ v planes:
(v = vertical, h = horizontal)
σ vmirror plane C
3
principal axis
σ hmirror plane
C3
principal axis
σ v mirror plane
contains the C3 axis
σ h mirror plane
is at right angles to theC3 axis
Mirror planes (σ) of BF3:
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C6
principal axis
C2
C2
C2C6C2
σ v σ v
σ h
C6
principal axis
C6
principal axis
Rotational axes and mirror planes of benzene
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• 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).
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center of symmetry center of symmetry
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• Improper rotation (Sn)
Rotation by 2π
/n followed by reflectionσ
,⊥
to the rotation axis.Since performing σ two times is the same as doing nothing (E), therefore S
can only be performed odd number of times.
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• 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
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Types of matrices:
Rectangular Matrix
Column Matrix
Row matrix
Zero null matrix
Square matrix
Diagonal Matrix
Scalar Matrix
Unit or Identity Matrix
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Equal Matrices:
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Direct product of two matrices:
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Trace or Character of a matrix
Trace or character of matrix is the sum of the diagonal elements.It is represented by “
” .
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E or Identity Matrix:
E(x1 ,y1 ,z1) = (x1 ,y1 ,z1)
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σ
Matrix: σxz (x1 ,y1 ,z1) = (x1 ,-y1 ,z1)
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Plane of symmetry (σ
) Matrix:
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σ
Matrix:
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Inversion (i) Matrix:
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Inversion (i) Matrix:
Therefore, the inversion (i) matrix is:
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Cn Matrix:
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x2 = r [cosθ
cos + sinθ
sin ]
x2 = r [sin θ cos - cos θ sin ]
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Sn Matrix:
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Sn Matrix:
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E C2 σxy i
The following matrices form a representation of the C2h point group
The following matrices form a representation of the C3v point group→
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• 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.
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Defini tion of a group
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Group Multiplication table for C2h:
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• 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 Sn
m axes are in a class. If there are two or many such
types they are placed in as many classes.
• Similar vertical (σv) and similar dihedral planes (σd) are in a class.
• Horizontal plane (σh) is a special plane and is always placed in a
different class from other planes.
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• 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.
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• In symmetry, a point group is the collection of symmetry operations that leaves amolecule 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)
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B2Br 4 has the following staggered structure:
Ga2H6 has the following structure in the gas phase: