Dr.
James Matshwele
Office: 237/246
Email: [email protected]
CHE 322: Tel: 355 2486
GROUP
THEORY
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CHE322 - Group Theory
• Learning material on Moodle
• Assessment Continuous assessment (50%)
and Final Examination /Term Paper) (50%)
• 1 Quiz 25% 1 Test 25% + 50%
• Whatsapp Group
• Class Attendance
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Chapter 1: Introduction to Symmetry Elements
and Operations
1.1. Definitions of symmetry elements and
operations
1.2. How to identify symmetry elements and
operations
1.3. Illustrations of how symmetry operations
are carried out on objects
1.4. How symmetry operations are combined
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Chapter 1: Introduction to Symmetry Elements
and Operations
Group Theory:
Group theory in chemistry decodes molecular symmetries using
mathematical groups, predicting and explaining molecular properties,
physical behavior, and guiding material design.
A symmetry Element:
Intrinsic property of an object
Necessary for a symmetry operation to be carried out
A symmetry Operation:
It is an action that when carried out on an object (molecule), the state of
the object after the said action is indistinguishable (not identical) from its
state before the action.
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Symmetry Elements and Operations
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Identity Element (E)
DO NOTHING!
Scheme 1: An operation of E to the Ru(III) complexes
All molecules have the identity element.
The identity operation is doing nothing to the molecule
(It doesn’t rotate, reflect, or invert...it just is)
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Cn Proper Rotation (C)
A ‘’proper’’ rotation is just a simple rotation operation about an axis. The
C
symbol for any proper rotation or proper axis is 360/n, where n is the
degree of rotation. Thus, a 180 rotation is a C2 rotation around a C2 axis,
and a 120 rotation is a C3 rotation about a C3 axis.
ROTATION BY 360/n
Scheme 2: Operation of rotation on the Ru(III).
PRINCIPLE AXIS : The principle
axis of a molecule is the highest
order proper rotation axis. For
example, if a molecule had C2
and C4 axes, the C4 is the principle
axis.
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Mirror Plane (σ)
Symmetry planes are mirror planes within the molecule. A reflection operation
occurs concerning a plane of symmetry.
σv
σh
REFLECT
OBJECT IN A
PLANE
Scheme 3: Operation of σv Scheme 3: Operation of σh
There are three classes of symmetry elements:
1-σv(vertical): vertical planes are parallel to the principal axis
2-σh(horizontal): horizontal planes are perpendicular to the principal axis
3-σd(dihedral): dihedral planes are parallel to the principle axis and bisect two C2' axes
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Inversion Centre (i)
INVERSION
SYMMETRY
Scheme 4: Operation of inversion
The inversion operation requires a point of symmetry (a
center of symmetry within a molecule) In other words, a
point at the center of the molecule that can transform x,y,z
into x, y, z) coordinate.
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Improper Rotation Axis (Sn)
ROTATION
COMBINED
WITH MIRROR
Scheme 4: Operation of S4 Cn ⊥ σ
Improper rotation is a combination of a rotation with respect
to an axis of rotation (Cn) followed by a reflection through a
plane perpendicular to that Cn axis. In short, an S n operation
is equivalent to Cn followed by σh
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Combining Symmetry Operations: Rotations
• Note: C42= C2, so C42 is not
counted as a symmetry
operation possible for this
object.
• C43 is a unique operation and is
therefore listed as one of the
symmetry operations for this
object
• C44 takes the object to its initial
state. It has the same effect as
having done nothing to the
object, therefore
• C44 = E
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Combining Symmetry Operations: Rotations
• An alternative way of writing
the operation C42 is C4C4 C4C4 = C2
meaning a 90o clockwise Check it out!
rotation was carried out, and
then followed by another.
• Similarly, σ2 can be
σvσv = E Check it out!
represented as σσ meaning a
reflection followed by another
reflection by the same mirror What about σσ’ ?
plane Is it the same as
σ’σ
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Combining Symmetry Operations: Rotations
• What about σσ’ ? Is it the
same as σ’σ
• σ'vσv = σv
• Does σvσv' = σv give the same
result?
• YES: σvσv' = σ'vσv = σv
• So, σ’v & σv are said to
commute with each other, or
to be commutative
operations
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Combining Symmetry Operations: Rotations
• What about σσ’ ? Is it the same
as σ’σ
• σ'vσv = σv
• Does σvσv' = σv give the same
result?
• YES: σvσv' = σ'vσv = σv
• So, σ’v & σv are said to commute
with each other, or to be
commutative operations
• EXERCISE: Check out C2 and
σv using the same diagram in
the slide.
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Combining Symmetry Operations: Rotations
• But do operations always commute?
C3σv = σv'
σvC3 = σv’’
• The product of a combination of symmetry operations for an object is always one of the
symmetry operations for the object
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Combining Symmetry Operations: Reflections
• σvσ’v = C3
• σ'vσv = C32
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THANK
YOU
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Examples of Symmetry Operations
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