Molecular symmetry

Can be used to predict IR spectra, to describe the types of orbitals used in bonding, to predict the optical
activity, to interpret electronic spectra and to study a number of additional molecular properties

Group theory systematic treatment of symmetry

Symmetry operation is an action, such as rotation through a certain angle that leaves the molecule apparently
unchanged.

Symmetry element is a point, a line or a plane with respect to which the symmetry operation is performed.

Important symmetry operations and symmetry elements

Symmetry element Symmetry operation Symbol
Identity E
n-fold symmetry axis Rotation by 2/n Cn
Mirror plane Reflection
Center of inversion Inversion i
n-fold axis of improper rotation Rotation by 2/n followed by
reflection perpendicular to rotation Sn
axis

Identify operation, E leaves the whole molecule unchanged.

n-fold rotation is a symmetry operation if the molecule appears unchanged after rotation by 360 o/n. The
corresponding symmetry element is a line, the n-fold rotation axis, Cn, about which the rotation is
performed.
The reflection of a water molecule in either of the two planes is a symmetry operation; the corresponding
symmetry element the plane of the mirror (a mirror plane),
o The planes are vertical, in the sense of being parallel to the rotational axis of the molecule, labeled
with a subscript v, as in v.
o The benzene molecule also has a mirror plane, h, in the plane of the molecule. The subscript
signifies that the plane is horizontal in the sense that the principal rotational axis of the molecule is
perpendicular to it. d, for the planes that bisect the angle between the C atoms; d denotes
dihedral; v, for the plane that pass through the C atoms of the ring
Inversion
o Center of inversion, i = the symmetry element, the point through which the projections are made.

1
2 6
5 4
3
4 3 5
2
6
1

Improper rotation consists of a rotation of the molecule through a certain angle around an axis followed
by a reflection in the plane perpendicular to that axis. Example:
o CH4 fourfold improper rotation; 90o rotation about an axis bisecting two H-C-H bond angles,
followed by a reflection through a plane perpendicular to the rotation axis; denoted as S4.
o Is the corresponding combination of an n-fold rotational axis and a perpendicular mirror plane.
o S1 a rotation through a full 360o followed by a reflection in the horizontal plane; is equivalent to
a horizontal reflection alone; S1 and h
o S2 axis a rotation through 180o followed by a reflection in the horizontal plane is equivalent to
an inversion, i.

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Determination of point groups

1. Determine whether the molecule belongs to one of the special cases of low or high symmetry.
a. Low symmetry
i. C1 no symmetry other than the identity operation, CHFClBr
ii. Cs - only one mirror plane, H2C = CClBr
iii. Ci only an inversion center; few molecular examples, HClBrC- CHClBr (staggered)

b. High symmetry
i. C - linear molecules lacking an inversion center such as HCl
ii. Dh linear molecules having a center of inversion
iii. Td 4 C3 axes, 3 C2, 3S4 axes and six d planes
iv. Oh 4C3 rotations, 3C4 rotations and an inversion
v. Ih 6 C5 axes; total of 120 symmetry operations

2. Find the rotation axis with the highest n, the highest order Cn axis for the molecule. This is the principal
axis of the molecule. Ex. PF5 (C3), NH3 (C3), [Co(en)3]3+, (C3), 1,5-dibromonaphthalene (C2)
3. Does the molecule have any C2 axes perpendicular to the Cn axis? NH3 (no), PF5 (yes), [Co(en)3]3+ (yes),
1,5-dibromonaphthalene (no)
a. Yes D groups
b. No C or S groups

4. Does the molecule have a mirror plane (h horizontal plane) perpendicular to the Cn axis?
a. Yes Dnh groups (PF5 is D3h) or C and S groups (1,5-dibromonaphthalene is C2h)
b. No Dn or Dnd ([Co(en)3]3+ or Cn, Cnv or S2n (NH3, H2O2)

5. Does the molecule have any mirror planes that contain the Cn axis?
a. Yes - Dnd (CH3CH3, staggered) is D3d or C and S groups (NH3 is C3v)
b. No Dn ([Co(en)3]3+ is D3 or Cn or S2n (H2O2)

6. Is there an S2 axis collinear with the Cn axis?

a. Yes S2n; 1, 3, 4, 7-tetrafluorocyclooctatetraene
b. No Cn; H2O2 is C2

D Classifications C classifications
General case: Look for Cn axes nC2 axes Cn axis No C2 axes Cn axis
perpendicular to the highest order Cn
axis

Subcategories:

If a horizontal plane of symmetry Dnh Cnh

exists
If n vertical planes exist Dnd Cnv
If no planes of symmetry exist Dn Cn

Examples: Determine the point group of the following compounds: a) XeF4 b) IOF3 c) SF4

Applications of Symmetry
Construction and labeling of MO
To use the group to decide whether a molecule is polar or chiral

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Polar Molecules
a molecule with a permanent electric dipole moment

1. A molecule cannot be polar if it has a center of inversion. Inversion implies that a molecule has matching
charge distributions at all diametrically opposite points about a center.
2. A dipole moment cannot lie perpendicular to any mirror plane or axis of rotation that the molecule may
possess.
3. A molecule cannot have an electric dipole moment perpendicular to any axis of rotation.
4. Any molecule that has a Cn axis and either a C2 axis perpendicular to that Cn axis or a h plane
perpendicular to the axis cannot have a dipole moment in any direction.
5. Any molecule belonging to a D point group must be nonpolar. A BF3 molecule (D3h) is therefore nonpolar.
6. Molecules belonging to the tetrahedral, octahedral and icosahedral groups have several perpendicular
rotation axes that rule out dipoles in all three directions, so such molecules must be nonpolar; hence, SF 6
(Oh) and CCl4 (Td) are nonpolar.

Chiral molecules
A molecule that cannot be superimposed on its own mirror image.
The group theoretical criterion of chirality is that a molecule should not have an improper rotation
axis, Sn. That is, molecules with either a mirror plane or a center of inversion have improper-
rotation axes and cannot be chiral. Groups in which Sn is present include Dnh, Dnd and some of the
cubic groups (Td and Oh).

The Symmetries of Orbitals

Character Tables and Symmetry Labels

Molecular orbitals of diatomic molecules are labeled , and so on. These labels refer to the
symmetries of the orbitals with respect to rotations around the principal symmetry axis of the molecule.
The same designations can be used for specifying orbitals by noting the local symmetry with respect to the
axis o f a given bond.

Symmetry labels linear combinations of atomic orbitals on symmetry-related atoms.

- combination A1s + B1s + C1s of the three H1s orbitals in NH3 and only the orbitals
of the same symmetry type on the N atom will have a nonzero net overlap with this
combination.

SALCs (symmetry-adapted linear combinations) of atomic orbitals the combinations of atomic orbitals of
a specified symmetry from which molecular orbitals are built.

a, a1, e, eg and so on molecular orbitals in nonlinear molecules, are based on the behavior of the orbitals
under all the symmetry operations of the relevant molecular point group.

Character table of the group a table that characterizes the different symmetry types possible in a point
group
C2 (rotation by 180o)
+1 no change of sign
-1 change of sign

Example: C2v character table

E C2 v (xz) v (yz)
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

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 Character, - the entries in a complete character table are derived by using the formal techniques of group
theory
The columns in a character table are labeled with the symmetry operations of the group
The rows, which summarize the characteristic symmetries of orbitals are labeled with the symmetry type

Interpretation of character tables

Entries under E indicate the degeneracy of the orbitals

Character Significance
+1 The orbital is unchanged
-1 The orbital changes sign
0 The orbital undergoes a more
complicated change

Example: consider 2Px orbital on the O atom of H2O

C2 = -1

'
v

= -1

In a C2v molecule such as water, the 2Px orbital on the central atom changes under a C2 rotation which
signifies that it is a B orbital. That it also changes sign under the reflection v identifies it as B1.

Construction of Molecular orbital

M. O.s are constructed from symmetry-adapted linear combinations of atomic orbitals of the same
symmetry type
In a linear molecule with the z-axis as the internuclear axis, an s orbital and a Pz orbital both have
symmetry and so may combine to form molecular orbitals.
An s orbital and a Px orbital have different symmetries ( and , respectively) and hence cannot contribute
to the same MO
The H1s orbitals in H2O (C2v) form two SALCs; + = A1s + B1s and - = A1s - B1s. Under C2, +
does not change sign but - does; their characters are +1 and -1, respectively. Under the reflections, +
does not change sign; - changes sign under v, so that its character is -1 for this operation. The characters
are therefore:

E C2 v v
+ 1 1 1 1
- 1 -1 -1 1

Symmetry types = A1 and B2

The O 2s and O 2Pz orbitals also have A1 symmetry. O 2Py has B2 symmetry, the linear combinations that
can be formed are:

a1 = c1O 2s + c2O 2Pz + c3+ (the 3 a1 orbitals are bonding, intermediate and antibonding in character)
b2 = c4O 2Py + c5 - (one of the two b2 orbitals is bonding and the other is antibonding)

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 Symmetry analysis has nothing to say about the energies of orbitals other than to identify degeneracies.
The general procedure for constructing a MO scheme for a reasonably simple molecule can be
summarized as follows:
o Assign a point group to the molecule
o Look up the shapes of the SALCs
o Arrange the SALCs of each molecular fragments in increasing order of energy, first noting
whether they stem from s, p or d orbitals (and put them in the order s < p < d) and then the number
of internuclear nodes.
o Combine SALCs of the same symmetry type from the two fragments, and from N SALCs form N
molecular orbitals.
o Estimate the relative energies of the MO from considerations of overlap and relative energies of
the parent orbitals, and draw the levels on a MO energy level diagram.
o Confirm, correct and revise this qualitative order by carrying out a molecular orbital calculation
using commercial software

The Symmetries of Molecular vibrations

z
z y

O x
y
H H x
x
y
z

H2O has a C2v point group;

nonlinear: 3N 6, therefore 3 vibrational modes
Character table for C2v point group

C2v E C2 v (xz) v (yz)

A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz
9 -1 3 1

Determine the irreducible representation

o E = all nine vectors are unchanged in the identity operation
o C2 = H atoms change position in a C2 rotation
= O atom vectors in the x and y directions are reversed; z direction remains the same
o v (xz) = reflection in the plane
= changes direction of all the y vectors; leaves x and z unchanged
o v (yz) = reflection perpendicular to the plane of the molecule
= the molecule changes the position of hydrogens; x vector of O atom changes while y
and z vectors remain unchanged
Reduce representations to irreducible representation

# of irreducible representations of a given type = 1/ order [(# of operations in the class) x

(character of reducible representation) x
(character of irreducible representation )]
Reducible representation: 3A1 + A2 + 3B1 + 2B2 equation (1)
Determine translational motions along the x, y and z directions: A1 + B1 + B2
Determine rotational motions in the 3 directions (Rx, Ry, Rz): A2 + B1 + B2

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 Get the summation: A1 + A2 + 2B1 + 2B2 equation (2)
Subtract (2) from (1): 2A1 + B1
Determine whether vibrational modes are either Raman or IR active
o Raman active: x2, y2, z2, xy, xz, yz or x2 y2
o IR active: x, y, z
o Vibrational modes for water are all IR and Raman active

3652/cm 1595/cm 3756/cm

Symmetry considerations

o A Raman transition can occur when the polarizability of a molecule changes during a vibration.
o Absorption of IR radiation can occur when a vibration results in a change in the electric dipole moment of a
molecule

The Exclusion rule

a. If a molecule has a center of inversion, one of its modes can be both IR and Raman active.
b. A vibrational mode is IR active if it has the same symmetry as a component of the electric dipole
vector.
c. A vibrational mode is Raman active if it has the same symmetry as a component of the molecular
polarizability.

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