CHEM 4123 Symmetry (MFT Ch. 4.

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LECTURE 02

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Symmetry in nature

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Human-derived symmetry in architecture

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 Other examples

Mathematical symmetries of fractal objects, helices, and lattices

(repeating patterns)are different than those of symmetric objects
Point vs. space symmetry 4
 Symmetry: some terminology
An object can have zero, one, or
many symmetry elements
a geometric, spatial object such as
a point, a line, or a plane
A symmetry operation is a
transformation of a molecule
about the symmetry element
Examples
bilateral symmetry of the Taj
Mahal
rotational symmetry of the purple
flower
An object is symmetric about
the element under the
operation if and only if the
object is indistinguishable before
and after the operation.
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 Symmetry operations for molecules
We want to identify all of the symmetry elements and
operations in objects.
Why? Symmetry tells us about the chemistry of
molecules
vibrational modes, bonding, reactivity, color, etc.
particularly important in inorganic compounds, as nature
repeats the same symmetries
To proceed
Learn the mathematical and geometrical definitions of the
symmetry elements and operations relevant to molecules
Practice (and practice and practice and ) identifying all of
the symmetry operations for particular molecules
The set of symmetry operations for a given molecule form
a point group
Five symmetry operations, four symmetry elements
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Operation #1: Identity (E)
The identity operation
means do nothing
Mathematically: multiply by
one
E is required for
completeness of the group
group theory (save this for
later)
Trivial: All objects have are
symmetric about the
identity operation
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 Operation #2: Proper Rotation (Cn)
A proper rotation is one
where the object is rotated
by 2/n (or 360/n) where n
1
n=1? rotate the object by
360, trivially symmetric
(equivalent of E)
n=2? rotate the object by
180: H2O
the example has a C2 proper
rotation axis, or C2 axis for
short
n=3? rotate by 120: CH4
n=4? rotate by 90: XeF4
n=5? rotate by 72: starfish
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 Example: simple snowflake

The algebra of operators

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What is n for the snowflake?
 Example: simple snowflake
Are there any other proper
rotation axes of symmetry
through the snowflake?
Six C2 axes perpendicular to
the C6 axis
three along arms of
snowflake
three in between arms of
snowflake
n: order of symmetry
Principal axis: the proper
rotation axis with the
highest order of symmetry
(largest n)
the C6 axis is the principal
axis of the snowflake

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Mathematical property of proper rotations
Any object with a Cn axis must have either
zero or n perpendicular () C2 axes
Example: pentagon

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Mathematical property of proper rotations
Any object with a Cn axis must have either
zero or n perpendicular () C2 axes
Example: pentagon of arrows

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 Molecular Example: staggered ethane

What is an obvious axis of

proper rotational symmetry?
C3 axis: is this the principal axis?
C3 axis: how many C2 can this
molecule have?
Zero or Three. Which is it?
Zero or Three. Where are they?

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Molecular Example: staggered ethane

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 Operation #3: Reflection ()
A reflection is a transformation
through a mirror plane
exchange of left-right, point moved
perpendicularly through the plane
on the other side
Example: human body
bilateral symmetry (ignoring
details, etc.)
h : horizontal mirror plane is to
the principal axis
v or d : vertical or dihedral mirror
plane is to the principal axis
Linear objects have an infinite
number of mirror planes through
the center line of the of the
object 15
 Molecular Example: dichlorobenzene

1,4 dichlorobenzene
Proper rotation axis?
How many?
Mirror planes?
Where? What kind?

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 Molecular Example: dichlorobenzene

1,2 dichlorobenzene
Proper rotation axis?
How many?
Mirror planes?
Where? What kind?

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 Operation #4: inversion (i)
Inversion is a
transformation where
each atom passes
through a point called a
center of inversion
Mathematically, if the
center of inversion is
defined as the origin of
the object, each point of
the object (x,y,z) is
transformed to (-x,-y,-z)
An object that is
symmetric about a
center of inversion is
looks unchanged after
applying the operation
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 Geometric example

The letter S? YES

The letter N? YES
The letter M? NO
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 Molecular Example: dichlorobenzene

1,4 dichlorobenzene
Inversion center?
1,2 dichlorobenzene
Inversion center?

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 More general geometries

Even orders: Squares, rectangles, parallelograms,

rectangular solids, octahedron, etc. HAVE inversion
centers
Odd orders: tetrahedra, triangles, pentagons DO
NOT have inversion centers
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 Operation #5: improper rotation (Sn)

An improper rotation (or rotoreflection) operation

is a 360/n rotation about an axis followed by reflection
through a plane perpendicular to the axis
Example: S4 axis of methane (Figure 4.6 MFT) 22
 Operation #5: improper rotation (Sn)

The coincident equivalences of improper rotations

and proper rotations for methane 23
 Summary symmetry operations
Identity (E) the do nothing operation
Proper rotation (Cn) rotation of 360/n about an axis
the axis with the largest order of symmetry n is the principal axis (sometimes
many with the same order)
the molecule can have either zero or n C2 axes perpendicular to the principal
axis
Reflection () translation of each part through a plane (mirror symmetry)
h: mirror plane is perpendicular to principal axis (h = horizontal)
v or d: mirror plane contains the principal axis (v = vertical, d = dihedral)
Inversion (i) transformation through a point
center of inversion
Improper rotation (Sn) - rotation of 360/n about an axis, followed by a
reflection through a plane perpindicular to the axis

A molecule is symmetric about one of these operations if it remains

indistinguishable before and after applying the operation
Algebra of operations: chaining symmetry operations together
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 Practice - staggered ethane
We discussed the staggered
ethane molecule as an example of
proper rotations.
Lets walk through each operation
and identify which symmetries
apply to the molecule
What is the easiest symmetry to
assign to any molecule?
The identity E
Recall our discussion of the C3 (+
C32)and 3C2 axes (C2, C2, C2)
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Practice - staggered ethane

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 Practice - staggered ethane

Running list: E, 2 C3, 3 C2

What about mirror planes? Does it have reflection symmetry?
Does the plane contain the principal axis?
Does the plane bisect twoC2 axes?
d, d, d
Is there a horizontal plane? 27
 Practice - staggered ethane

Running list: E, 2 C3, 3 C2, 3 d

What about inversion? Is there a center of inversion?
There is an inversion center at the center of the C-C bond
More? No. A molecule can only have at most one center of
inversion 28
 Practice - staggered ethane

Running list: E, 2 C3, 3 C2, 3 d, i

Improper rotation? easier to see if we number the H atoms
Proper rotation + reflection through perpendicular mirror
plane
S6 improper rotation axis 29
 Practice - staggered ethane

Running list: E, 2 C3, 3 C2, 3 d, i

Which improper rotation operations are unique?
S6, S65 = S6-1 30
 Practice - staggered ethane

Running list: E, 2 C3, 3 C2, 3 d, i, 2 S6

12 operations that describe the unique, complete symmetry of
staggered ethane
Also, for any molecule that looks like staggered ethane
Eclipsed ethane?
Molecules with identical geometries/symmetries, not identical
chemical formulas
Next lecture: Point groups as a mathematical description of
molecular symmetry 31