Ch 3.

Molecular Symmetry

Overview

1. Symmetry governs the physical and spectroscopic properties of

molecules and provide hints about how reactions might occur.

2. Group Theory: the systematic treatment of symmetry.

3. Symmetry operation: a fundamental concept of group theory.

4. Point Group: symmetrical description of molecules.

Symmetry helps us understand molecular structure, some chemical
properties, and characteristics of physical properties (spectroscopy) – used
with group theory to predict vibrational spectra for the identification of
molecular shape, and as a tool for understanding electronic structure and
bonding.
Why Symmetry?
Chemists classify molecules according to their symmetry. The collection of symmetry
elements present in a molecule forms a “group”, typically called a point group. Why is it
called a “point group”? Because all the symmetry elements (points, lines, and planes) will
intersect at a single point.

Example (water).
What symmetry elements does water possess? Identity, E; two reflection planes, σxz and σyz;
and one 2-fold rotation axis, C2. In the common notation (aka Schoenflies notation), this is
known as the C2v point group.

Another molecule that also belongs to the C2v point group is cyclohexane in the boat
conformation. They do contain the identical set of symmetry elements, even though their
overall shapes are quite different.

Determining Point Groups

So how does one determine the point group of a molecule? One possible approach is
simply to find all the symmetry elements and then look at a set of tables (character tables)
until you find a matching set. While this would not be hard for something as simple as
the example above, molecules like methane that contain 24 symmetry elements would be
more tedious!

So chemists have developed various flowcharts that make the process as simple as
answering a serious of yes/no questions.
3-1. Group

Rules for any set of elements to perform Mathematical group (ex, binary operation)

1. The product of two members and the square of any member is also a member of the group.
à if symmetry element A and B belong to a group, the product AB or BA belong to the
same group.

2. Every group must have an Identity operation E, which leaves all other elements unchanged.
à EX = XE = X

3. All operations of the group are Associative.

à ABC = (AB)C = A(BC)

4. Every operation must have a Reciprocal (Inverse) which is also an element of the group.

à in C4 operation case: C4-1 = C43

à AA-1 = E, if A is a member, A-1 must also be.

3-2. What is Group Theory?

1. Mathematical treatment of Symmetry

2. Group theory is the tool that is used to determine symmetry.

3. Symmetry of molecule, the symmetries of some local atoms, molecular orbitals, rotations
and vibrations of bonds.

4. For example,
- If the symmetries of molecular orbital wave functions are known, we can find out
information about the binding.
- by the selection rules that are associated with symmetries, we can explain whether
the transition is forbidden or not
- we can predict and interpret the bands we can observe in Infrared or Raman spectrum.

5. Symmetry operations and symmetry elements are two basic and important concepts in
group theory.
 3-3. Why Group Theory?

1. Predicting whether a given molecule will be chiral, or polar.

2. Examining chemical bonding and visualizing molecular orbitals.
3. Predicting whether a molecule may absorb light of a given polarization, and which
spectroscopic transitions may be excited if it does.
4. Investigating the vibrational motions of the molecule.
5. Predicting hybrid orbitals.
6. Predicting the contribution of atomic orbitals in the construction of molecular orbitals.
7. Predicting the d-d splitting pattern.
8. Predicting the particular electronic transition in UV spectrum (forbidden and/or allowed).
9. Predicting the number of peaks in IR and Raman spectrum.
10. Predicting the number of peaks in NMR and ESR (electron spin resonance) spectrum.
3-4. Group Theory and Chemistry

- Group Theory is a purely mathematical concept.

- Most of the fundamentals of group theory were developed by the French

mathematician Evariste Galois (1811 – 1832) in the early 19th century.

- The principles of Group theory are used by Chemists and Physicists for the analysis
of symmetry properties, structure, bonding and molecular spectra of compounds.
3-5. Symmetry Elements and Symmetry Operations

- A symmetry element is a geometric entity such as a line, a plane or a point about which
one can perform an operation of rotation, reflection or inversion.
- A symmetry operation is a movement of a molecule/object such that the resulting
configuration is indistinguishable from the original.
- During any symmetry operation at least one point in the molecule should remain unchanged. This
point is the center of gravity of the molecule.
- During translation (bodily movement from one point to another) the center of gravity of the
molecule is unchanged.
- Therefore, a molecule should never be translated during a symmetry operation.
- A symmetry operation will transform a molecule into an equivalent or identical
configuration. A symmetry element

Doing this is a
symmetry operation
3-5-1. Symmetry
(Def) Invariance to transformation: the object appears unchanged after transformation.

(1) Symmetry elements and symmetry operations

Symmetry element:
A geometric entity (line, point, or plane) about which some transformation may be
executed.
Axis = line Cn Plane s
Point I Plane + Axis Sn
1. The identity operation

2. Reflection in a plane

3. Rotation about an axis

In three dimensions, rotations about the x, y and z axes acting on a vector (x,y,z) are
represented by the following matrices.
Symmetry operation: the movement of a molecule relative to some symmetry element such that every
atom before the operation coincides with an equivalent atom after the operation.

(1) Axis of rotation (Cn): proper rotation axis invariant to rotation by some fraction of 2p
Cnm: n-fold axis of symmetry (rotation about the n-fold axis by 2pm/n radians)
matrix for a clockwise Cn operation

A symmetry element

Doing this is a
symmetry operation
 syz
(2) Mirror plane (s): reflection through the symmetry plane, (x, y, z) (-x, y, z) = (x’, y’, z’)

transformation equations for syz

in matrix notation

Three different types of mirror plane

i) sh : mirror plane normal to the principal proper rotation axis, h = horizontal mirror plane
ii) sn : mirror plane containing the principal rotation axis Cn, n = vertical mirror plane
iii) sd : mirror plane that bisects the dihedral angle made by Cn and two adjacent C2 axes
perpendicular the principal rotation axis, a special case of sn, d = dihedral mirror plane
(3) Improper rotation, or rotation-reflection axes (Sn):
Snm : rotation about the n-fold axis by 2pm/n radians, followed by reflection in the mirror plane
perpendicular to the n-fold axis or vice versa
matrix (Sn)z = sxy(Cn)z

S4

(4) Identity (E)

equivalent of doing nothing
(5) Center of symmetry (i): inversion operation: inversion through the center of symmetry
(x, y, z) → (-x, -y, -z)

Inversion center?
2. Summary
3. Combination of Symmetry Operations: group multiplication
à 2 continuous symmetry operations: always operate from the right one.
à A×B = “Do B and then A”

svC3 = sv’’

C3sv= sv’
Rule 1)
à 2개의 symmetry operation 결과가 순서에 관계없이 같게 나타나면
i.e.) A×B = B×A
à these two symmetry operations are “commute”.

C2 × 𝛔v’ = 𝛔v
𝛔v’ × C2 = 𝛔v

Thus, 𝛔v’ and C2 are commute.

result of reflection through s1 and s2 depends on the order => reflection operation do not commute
sC2 C2s

sC2 = C2s : commute

Rule 2)
à Symmetry operations follow associative law of multiplication.
i.e.) A(BC) = (AB)C

(s1s2)(s1s2) = (C4)(C4) = C2
s1(s2s1s2) = s1(s1’) = C2
(s1s2s1)s2 = (s2’)s2 = C2
associative: result does not depend on the choice of parentheses or the grouping of operations
II. Group

Rules for any set of elements to perform Mathematical group

1. The product of two members and the square of any member is also a member of the group.
à if symmetry element A and B belong to a group, the product AB or BA belong to the same
group.
2. Every group must have an Identity operation E, which leaves all other elements
unchanged.
à EX = XE = X
3. All operations of the group are Associative.
à ABC = (AB)C = A(BC)
4. Every operation must have a Reciprocal (Inverse) which is also an element of the group.

à in C4 operation case: C4-1 = C43

à AA-1 = E, if A is a member, A-1 must also be.

 svC3 = sv’’

C3sv= sv’

There are two important points that are illustrated by this example:

1. The order in which two operations are applied is important. For two symmetry operations A and B, AB
is not necessarily the same as BA, i.e. symmetry operations do not in general commute. In some
groups the symmetry elements do commute; such groups are said to be Abelian.

2. If two operations from the same point group are applied in sequence, the result will be equivalent to
another operation from the point group. Symmetry operations that are related to each other by other
symmetry operations of the group are said to belong to the same class. In NH3, the three mirror planes
σv, σv’ and σv’’ belong to the same class (related to each other through a C3 rotation), as do the
rotations C3+ and C3- (anticlockwise and clockwise rotations about the principal axis, related to each
other by a vertical mirror plane).

The effects of applying two symmetry operations in sequence within a given point group are
summarized in group multiplication tables.
II-1. Group Multiplication Tables ex) C2
C2v
Within a Symmetry Group,

1. The symmetry operations’ combinations can be summarized in a table so

that each Row and Column will have one and only one occurrence of each
symmetry operation !!

2. Number of Row and Column elements should be the same.

3. In the table, each elements is the product of Column and Row element.

4. Operation should be Column element first.

II-2. Subgroup
Within a group multiplication table,

(Def) A subset of Symmetry Operation’s within a group which itself a group.

e.g.) C2 ⊂ C2v , C2 is a subgroup of C2v
III. Point Group
Symmetry elements for square planar molecules:
à E, C4, C2(=C42), 4C2, s, 4s’, i, S4 regardless of the chemical
composition of the molecule.
Symbol for a square planar molecule = D4h

Triangular planar molecule BCl3

X = C3 axis
Y = C2 axes
Z = plane of symmetry

the principal C3 axis (taken to be vertical)

a horizontal plane (sh)
three C2 axes at right angles to the principal axis
III-1. Point group?

Ethane in the staggered conformation

III-2. Symmetry Operations for Square Based Pyramid AB5

* Initial and final orientations are

indistinguishable except for the (artificial)
numerical labels.
III-3. Symmetry Point Group
à Collection of all Symmetry Operations that may be carried out on a molecule of a specific symmetry. These will
have a common intersection, generally a Point.
(All point groups behave as any algebric group; Completeness, Identity element, Associative law, Reciprocals)

1. Cn, Cnv and Cnh Rotational Groups

1) Cn Point group à group with continuous proper axis Cn operation
(Cnm case; if m/n is divisor, divide it. à C64 = C32 )
Usually, molecules with Cn point group are optically active and have net dipole moment.

2) Cnv Point group à Cn + n𝛔v (mirror plane which contains principal Cn rotational axis)
3) Cnh Point group à Cn + 𝛔h (horizontal plane perpendicular to Cn rotational axis)

4) C1 Point group à Only identity (E) symmetry operation is applicable.

5) Cs Point group à Group has only E (identity) and 𝛔h (plane symmetry) symmetry elements.

6) Ci Point group à Group has only E (identity) and i (center of inversion) symmetry elements.
2. Dn, Dnv and Dnh Dihedral Groups
1) Dn Point group à Cn + nC2 (axis perpendicular to Cn axis)
Usually, molecules with Dn point group are optically active and have zero dipole moment.

2) Dnh Point group à Dn + 𝛔h (horizontal plane perpendicular to Cn rotational axis)

3) Dnd Point group à Dn + 𝛔d (dihedral mirror plane bisecting adjacent C2 axes which are perpendicular to Cn axis)
3. Sn Group (Sn symmetry operation: Cn + 𝛔h )
1) For odd n :
Sn2n = E
Sn = Cnh (except S1 = Cs)
i.e.) Sn (n = odd) group, 2n operations are possible and changeable to Cn or Cnh
2) For even n:
Generally, Sn (even) group require Cn/2 axis.
ex) S6 case
S61 = 𝛔C6 = S6 S6 2 = 𝛔 2 C 6 2 = C 3
S6 3 = 𝛔 3 C 6 3 = i S6 4 = 𝛔 4 C 6 4 = C 3 2
S6 5 = 𝛔 5 C 6 5 = S6 5 S6 6 = 𝛔 6 C 6 6 = E
S6 point group’s full element set is
S6 C3 i C3 2 S6 5 E
Pure Sn (n = even) groups are possible. (S4 S6 S8 )
Platonic solids
all vertices, edges, and faces are equivalent
the tetrahedron, the octahedron, the cube, the regular dodecahedron (with pentagonal faces), and the icosahedron
-rotation subgroup (eliminating all operations except Cn) : I, T, O
-full symmetry group : Ih, Td, Oh
-cube and octahedron have the same symmetry elements belonging to the Oh group
 Oh

D3h

C3v
Cubic symmetry
à Td and Oh.
à Closely related to the
symmetry of a cube.

Icosahedral group, Ih.

à Icosahedron.
Td à 12 C5s.

Oh

C60
C540
 Application of Symmetry
Applications: the construction and labeling of molecular orbitals.
the interpretation of spectroscopic data to determine structure.

to decide whether a molecule is polar or chiral.

2-3. Polar Molecules
Polar molecule contains a permanent electric dipole moment.

àA molecule cannot be polar; if it contains the group D.

if it contains a center of inversion.
if it contains the cubic groups (T, O, I).

Center of inversion: a molecule has matching charge distributions at all diametrically opposite
points about a center.
à rules out a dipole moment.

Group D (C, ⊥C, σ): a dipole moment cannot lie perpendicular to any mirror plane of
axis of rotation that the molecule has.

Therefore, 1. a molecule cannot be polar if it has a center of inversion.

2. a molecule cannot have an dipole moment perpendicular to any mirror
plane.
3. a molecule cannot have an electric dipole moment perpendicular to any
axis of rotation.
 Circular Dichroism; refers to the differential absorption of left and
2.4. Chiral molecule right circularly polarized light.
Optical Rotatory Dispersion; is the variation in the optical rotation
of a substance with a change in the wavelength of light.

Enantiomers & optically active (CD, ORD) à Absolute configuration

àA molecule cannot be chiral; if it contains an improper rotation axis (Sn)
àMolecules w/ either a mirror plane or a inversion center
à contain improper rotation axis
à cannot be chiral.
Optical isomers à Chiral à enatiomeric pair

Chiral molecules are optically active.

One eneatiomer rotates the plane of
polarized light in one direction and
the other one rotates it through an
equal angle in the opposite direction.

CD & ORD
Circular Dichroism
Optical Rotary Dispersion
III-4. Application of Symmetry
C3

Linear groups (C¥n and D¥h)

C¥n : no C2 axis perpendicular to the C¥ axis

CO, HCN
D¥h : C2 axis perpendicular to the C¥ axis
OCO, HCCH
Assign the following species to rotation groups and to full symmetry groups
Problem) Determine the point group.