Dr.

James Matshwele
Office:
Email: [email protected]
Tel: 355 2486
CHE 322: Cell:
GROUP Office: 237/246
THEORY
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 Chapter 3: Lecture 7: Representations and
Character Tables

Non-degenerate Representations :

Definition of a representation and its illustration.

Introduction to the reduction formula and its application to
decompose reducible representations into irreducible
representations (irreps).

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 Chapter 3: Lecture 7: Representations and
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.
http://mutuslab.cs.uwindsor.ca/macdonald/250-LectureNotes/Fall2002/Bonding-Notes5.pdf

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Chapter 3: Lecture 7: Representations and
Character Tables

The functions to the right are called basis

functions. They represent mathematical functions
such as orbitals, rotations, etc.

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3: Lecture 7: Representations and
Character Tables – 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.

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 Chapter 3: Lecture 7: Representations and
Character Tables – 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.

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Chapter 3: Lecture 7: Representations and
Character Tables – 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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 Chapter 3: Lecture 7: Representations and
Character Tables – The Px Orbital

If a px orbital on the central atom of a molecule with C 2v

symmetry is reflected in the yz plane, the orbital is also
reversed, and the character will be -1.

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 Chapter 3: Lecture 7: Representations and
Character Tables – The Px Orbital

If a px orbital on the central atom of a molecule with C 2v

symmetry is reflected in the xz plane, the orbital is unchanged, so
the character is +1.

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3 : Lecture 7: Representations and
Character Tables

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 Chapter 3: Lecture 7: Representations and
Character Tables
Interpreting symmetry labels and characters:

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Chapter 3: Lecture 7: Representations and
Character Tables
The d-Orbitals and their special disposition

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Chapter 3: Lecture 7: Representations and
Character Tables

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Chapter 3: Lecture 7: Representations and
Character Tables

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 Chapter 3: Lecture 7: Representations and
Character Tables

Strictly speaking, the representations are characters of the operator matrices that that represent
the operations

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 Determining Point Groups
• HCl
• HClBrC-CHClBr
• CO2
• SF6
• PF5
• H2O2
• H3CCH3
• NH3 • 1,5-dibromonaphthalne
• CH4 • 1,3,5,7-
• CHFClBr
tetrafluorocyclooctatetraene

• H2C=CClBr • B12H122-
THANK
YOU

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 Dr. James Matshwele
Office: 237/246
Email: [email protected]
CHE 322: Tel: 355 2486
GROUP
THEORY
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 Chapter 3: Lecture 8: Representations and
Character Tables Cont..
Interpretation of Representations using Matrices

• Information about the symmetry aspects of point groups are summarized in character tables. Character
tables can be thought of as shorthand versions of matrices that are used to describe symmetry aspects of
molecules.
• A matrix is an ordered array of numbers represented in columns and rows.
• Each character in a non-degenerate representation can be regarded as a representative 1x1 matrix, M for
each of the operations within a point group.

• So, the C2 operation can be represented by the mathematical operator 1, which is a 1 x 1

matrix
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 Chapter 3: Lecture 8: Representations and
Character Tables Cont..
Interpretation of Representations using Matrices - the effect of C2 on a Px orbital?
C2x Px= -Px

Mathematically:
C2 = -Px

Meaning:
C2 = Oprator matrix -1,
which is a 1x1 ,matrix.
The 1x1 matrix is said to be a 1-
dimentional matrix. The reason it is 1-
dimentional (as opposed a 2x2, or 2-
dimentional matrix, for example) is that
there is only one entity (the direction of
the Pxorbital) that is being used as the
basis for the analysis of the effect of the
operation

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 Chapter 3: Lecture 8: Representations and
Character Tables Cont..
Let's consider a C2V Point group and derive matrix reps for p-orbitals as a basis.

C2V E C2 σ(xz) σ(yz) Rep

Px 1 -1 1 -1 B1
Py 1 -1 -1 1 B2
Pz 1 1 1 1 A1

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 Chapter 3: Lecture 8: Representations and
Character Tables Cont..
• Representations of 1-dimentional matrices are
called irreducible representations (irreps).
ADDING IRREDUCIBLE • This means they can be reduced, to form reducible
REPRESENTATIONS representations.
• Reducible can be understood as summations of
irreducible representations, as illustrated below
• Consider the summation A1 + A2 + B2
A1 1 1 1 1 +
A2 1 1 -1 -1 +
B2 1 -1 -1 1
Г= 3 1 -1 1
• Ge, ghe, or he Г is called a reducible representation
because it can be reduced into A1, A2 and B2
And so we can write;

Г = A1 + A2 + B2

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 Chapter 3: Lecture 8: Representations and
Character Tables Cont..
ADDING IRREDUCIBLE REPRESENTATIONS and Reduction of Reducible representations
• Representations of 1-dimentional matrices are Normally, Group Theory problems
called irreducible representations (irreps). involve
• This means they can be reduced, to form 1. Finding a reducible representation for
the problem at hand
reducible representations. 2. Reducing the reducible
• Reducible can be understood as summations of representation into its component
irreducible representations, as illustrated below reducible reps
3. Interpreting the results of the
• Consider the summation A1 + A2 + B2
reduction
A1 1 1 1 1 + 4. The vital information in Group
Theory is therefore contained in
A2 1 1 -1 -1 +
the reducible representation.
B2 1 -1 -1 1 Identifying the correct reducible
Г= 3 1 -1 1 representation is therefore a key
• Ge, ghe, or he Г is called a reducible representation step in solving a Group Theory
because it can be reduced into A1, A2 and B2 And problem.
so we can write; Г = A1 + A 2 + B2
• how would you reduce it to its irreducible
representations?
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THANK
YOU

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 Chapter 2: Lecture 11:

Matrices and their multiplication

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.

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