M.Sc.
Semester-II
Compulsory Paper-7 (CP-7)
Group Theory and Spectroscopy
I. Symmetry and Group Theory in Chemistry
Lecture 3 : Character Table, Character Table for C2v Point
Group
Dr. Rajeev Ranjan
University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi
Symmetry and Group Theory in Chemistry : 25 Hrs
Symmetry elements and symmetry operation, Group and Subgroup, Point group, Classification and
representation of groups, The defining property of a group, Sub group and Class, Group multiplication table
for C2V, C2h and C3V point group, Generators and Cyclic groups. Similarity Transformation, Table of
conjugates for C2V, C2h and C3V point group, Schonflies symbols.
Matrix notation for symmetry operation, Representations of groups by matrices (representation for the Cn,
Cnv, Cnh and Dnh groups to be worked out explicitly). Character of a representation, Mulliken symbols for
irreducible representations, Direct product relationship, Applications of group theory to quantum
mechanics-identifying non-zero matrix elements.
The great orthogonal theorem (without proof) and rules derived from this theorem. Derivation of the
orthonormalization condition. Character table. Construction of character table: C2V and C3V (only).
Reducible representations and their reduction. Total character and their calculation. Application of
character table in determination of IR and Raman active vibrations: H2O, BF3 and N2F2
Coverage:
1. Character Table
2. Character Table for C2v point group
3. Representations of Symbols
4. Applications of Group Theory
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Lecture 3 : Character Table, Character Table for C2v Point Group
Character Tables
The symmetry properties of each point group are summarized on a
character table. The character table lists all of the symmetry elements of
the group, along with a complete set of irreducible representations.
Character Table (C2v)
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Lecture 3 : Character Table, Character Table for C2v Point Group
Character Table (C2v)
The functions to the right are called basis functions. They represent
mathematical functions such as orbitals, rotations, etc.
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Lecture 3 : Character Table, Character Table for C2v Point Group
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Lecture 3 : Character Table, Character Table for C2v Point Group
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Lecture 3 : Character Table, Character Table for C2v Point Group
The px orbital
If a px orbital on the central atom
of a molecule with C2v symmetry
is rotated about the C2 axis, the
orbital is reversed, so the
character will be -1.
If a px orbital on the central atom of a molecule with C2v symmetry is
rotated about the C2 axis, the orbital is reversed, so the character will be -1.
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Lecture 3 : Character Table, Character Table for C2v Point Group
The px orbital
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Lecture 3 : Character Table, Character Table for C2v Point Group
The px orbital
If a px orbital on the central atom
of a molecule with C2v symmetry
is reflected in the yz plane, the
orbital is also reversed, and the
character will be -1.
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Lecture 3 : Character Table, Character Table for C2v Point Group
The px orbital
If a px orbital on the central atom of a molecule with C2v symmetry is
reflected in the xz plane, the orbital is unchanged, so the character is +1.
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Lecture 3 : Character Table, Character Table for C2v Point Group
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Lecture 3 : Character Table, Character Table for C2v Point Group
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Lecture 3 : Character Table, Character Table for C2v Point Group
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Lecture 3 : Character Table, Character Table for C2v Point Group
Character Table Representations
1. Characters of +1 indicate that the basis function is unchanged by the
symmetry operation.
2. Characters of -1 indicate that the basis function is reversed by the
symmetry operation.
3. Characters of 0 indicate that the basis function undergoes a more
complicated change.
Representations of Symbols
1. An A representation indicates that the functions are symmetric with
respect to rotation about the principal axis of rotation.
2. B representations are asymmetric with respect to rotation about the
principal axis.
3. E representations are doubly degenerate.
4. T representations are triply degenerate.
5. Subscrips u and g indicate asymmetric (ungerade) or symmetric (gerade)
with respect to a center of inversion.
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Lecture 3 : Character Table, Character Table for C2v Point Group
Applications of Group Theory
1. Predicting polarity of molecules. A molecule cannot have a permanent
dipole moment if it
a) has a center of inversion
b) belongs to any of the D point groups
c) belongs to the cubic groups T or O
2. Predicting chirality of molecules. Chiral molecules lack an improper
axis of rotation (Sn), a center of symmetry (i) or a mirror plane (σ).
3. Predicting the orbitals used in σ bonds. Group theory can be used to
predict which orbitals on a central atom can be mixed to create hybrid
orbitals.
4. Determining the symmetry properties of all molecular motion
(rotations, translations and vibrations). Group theory can be used to
predict which molecular vibrations will be seen in the infrared or
Raman spectra.
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Thank You
Dr. Rajeev Ranjan
University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi
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