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GROUP THEORY
TONY FRANCIS
DEPARTMENT OF CHEMISTRY
St. MARY'S COLLEGE,
MANARKADU
Mathematical study of symmetry is called
Group Theory
• Symmetry Element– A symmetry element is a
geometrical entity such as a point, a line or a
plane about which a symmetry operation is
performed.
• Symmetry operation– A symmetry operation
is a movement such as inversion about a
point, rotation about a line or a reflection
about a plane in order to get an equivalent
orientation.
An equivalent orientation is an orientation similar to
the original orientation but not the identity.
Equivalent
orientation Identity
Symmetry Elements
Element Symmetry Operation Symbol
Identity E
Proper axis Rotation by 2π/n Cn
Plane of symmetry Reflection σ
Center of symmetry Inversion i
Improper axis of Rotation by 2π/n Sn
symmetry followed by reflection
perpendicular to the
axis of rotation
Identity, E
All molecules have Identity. This operation
leaves the entire molecule unchanged. A
highly asymmetric molecule such as a
tetrahedral carbon with 4 different groups
attached has only identity, and no other
symmetry elements.
Centre of symmetry (i)
• It is a point within the molecule from which
lines drawn to opposite direction meet similar
points at exactly the same distance and
direction.
Proper axis of symmetry
• It is an axis passing through the molecule
about which the molecule is rotated through
360◦, if we get n times equivalent orientations
the molecule has an n-fold axis of symmetry.
Principal axis
• If there are more than one axis of symmetry in many
cases one of the axis is identified as principal axis. The
selection will be on the following basis:-
1. Highest order axis
2. Unique axis
3. The axis passing through maximum no of molecule.
4. The axis perpendicular to the plane of the molecule
The other axis are known as subsidiary axis
Plane of symmetry
• Plane of symmetry is a plane which divide the
molecule into two equal halves such that one
half is the mirror image of the other half.
• On the basis of the principal axis they are of two
types vertical and horizontal plane.
• HP:-plane perpendicular to the principal axis(σh )
• VP:-plane which is along the principal axis or
involving the principal axis (σv )
Rotational axes and mirror planes of the water
molecule:
C2
principal axis
C2
C2σv
mirror plane
σv
mirror plane
The water molecule has only one rotational axis, its C2 axis,
which is also its principal axis. It has two mirror planes that
contain the principal axis, which are therefore σv planes. It
has no σh mirror plane, and no center of symmetry.
A rotation-reflection operation
(Sn) required
rotation of 360° /n, followed by
reflection through
a plane perpendicular to the axis of
rotation.
Equivalent and non-equivalent operations
14
O
H H
C2
sv
sv’
H
N
H
H
C3
sv
sv
sv
• sv : No atom moves
sv ‘: H atoms interchange
• sv : Two atoms move
Other two don’t
• sv and sv ‘ do not interchange by
C2
• The three sv planes interchange by
C3
Non-equivalent
planes
Equivalent planes
(Same class)
Boron trifluoride
C3
principal axis
C3
principal axis
σh
σh
σv σv
C2
C2 C2
boron trifluoride has a C3 principal
axis and three C2 axes, a σh mirror plane
three σv mirror planes, but no center of inversion
E,2C3,3C2,3σv,σh,2S3—D3h
Carbon dioxide-Dαh
E,C2,2C2,2σv,σh,i--- D2h
Ethene
C6
principal axis
C2
C2
C2
C6
C2
σv
σv
Rotational axes and mirror planes of benzene
σh
C6
principal axis
C6
principal axis
Ruthenium triethylenediamine
- Ru(en)3 - D3
Distinct operations
• D.O are operations that cannot be
represented by any other axis of lower
symmetry.
• Order- Total number of symmetry
operation
• Classes- It is the number of distinct
symmetry operations

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Introduction to group theory

  • 1. GROUP THEORY TONY FRANCIS DEPARTMENT OF CHEMISTRY St. MARY'S COLLEGE, MANARKADU
  • 2. Mathematical study of symmetry is called Group Theory • Symmetry Element– A symmetry element is a geometrical entity such as a point, a line or a plane about which a symmetry operation is performed. • Symmetry operation– A symmetry operation is a movement such as inversion about a point, rotation about a line or a reflection about a plane in order to get an equivalent orientation.
  • 3. An equivalent orientation is an orientation similar to the original orientation but not the identity. Equivalent orientation Identity
  • 4. Symmetry Elements Element Symmetry Operation Symbol Identity E Proper axis Rotation by 2π/n Cn Plane of symmetry Reflection σ Center of symmetry Inversion i Improper axis of Rotation by 2π/n Sn symmetry followed by reflection perpendicular to the axis of rotation
  • 5. Identity, E All molecules have Identity. This operation leaves the entire molecule unchanged. A highly asymmetric molecule such as a tetrahedral carbon with 4 different groups attached has only identity, and no other symmetry elements.
  • 6. Centre of symmetry (i) • It is a point within the molecule from which lines drawn to opposite direction meet similar points at exactly the same distance and direction.
  • 7. Proper axis of symmetry • It is an axis passing through the molecule about which the molecule is rotated through 360◦, if we get n times equivalent orientations the molecule has an n-fold axis of symmetry.
  • 8.
  • 9. Principal axis • If there are more than one axis of symmetry in many cases one of the axis is identified as principal axis. The selection will be on the following basis:- 1. Highest order axis 2. Unique axis 3. The axis passing through maximum no of molecule. 4. The axis perpendicular to the plane of the molecule The other axis are known as subsidiary axis
  • 10. Plane of symmetry • Plane of symmetry is a plane which divide the molecule into two equal halves such that one half is the mirror image of the other half. • On the basis of the principal axis they are of two types vertical and horizontal plane. • HP:-plane perpendicular to the principal axis(σh ) • VP:-plane which is along the principal axis or involving the principal axis (σv )
  • 11.
  • 12. Rotational axes and mirror planes of the water molecule: C2 principal axis C2 C2σv mirror plane σv mirror plane The water molecule has only one rotational axis, its C2 axis, which is also its principal axis. It has two mirror planes that contain the principal axis, which are therefore σv planes. It has no σh mirror plane, and no center of symmetry.
  • 13. A rotation-reflection operation (Sn) required rotation of 360° /n, followed by reflection through a plane perpendicular to the axis of rotation.
  • 14. Equivalent and non-equivalent operations 14 O H H C2 sv sv’ H N H H C3 sv sv sv • sv : No atom moves sv ‘: H atoms interchange • sv : Two atoms move Other two don’t • sv and sv ‘ do not interchange by C2 • The three sv planes interchange by C3 Non-equivalent planes Equivalent planes (Same class)
  • 15.
  • 16. Boron trifluoride C3 principal axis C3 principal axis σh σh σv σv C2 C2 C2 boron trifluoride has a C3 principal axis and three C2 axes, a σh mirror plane three σv mirror planes, but no center of inversion E,2C3,3C2,3σv,σh,2S3—D3h
  • 17.
  • 18.
  • 19.
  • 21.
  • 23.
  • 24.
  • 25.
  • 26. C6 principal axis C2 C2 C2 C6 C2 σv σv Rotational axes and mirror planes of benzene σh C6 principal axis C6 principal axis
  • 27.
  • 29.
  • 30.
  • 31.
  • 32.
  • 33.
  • 34.
  • 35.
  • 36.
  • 37. Distinct operations • D.O are operations that cannot be represented by any other axis of lower symmetry.
  • 38. • Order- Total number of symmetry operation • Classes- It is the number of distinct symmetry operations