Universidad del Valle

Inorganic Chemistry II

Prof. Renso Visbal Acevedo Departamento Química

email: renso.visbal@correounivalle.edu.co
 Molecular Symmetry
This will allow us to

• Classify atomic orbitals

• Construct hybrid orbital
• Classify molecular orbitals
• Classify the electronic states of the molecules
• Classify the vibrational modes
• Predict the allow transitions in electronic spectra
 Molecular Symmetry
Symmetry operations, elements and point groups
For qualitative effects, it is enough if we refer to the shape of a
molecule using terms like tetrahedron, square planar, octahedron, etc.
However, the use of these term is not always precise.

Symmetry operations are actions that leave the molecule apparently

unchanged.

F H
120º 120º 121º 121º
B B
F F F F
120º 118º
Trigonal Pseudotrigonal
Plana Plana
B-F = 131 pm B-H = 119 pm
 Molecular Symmetry
Symmetry operations and elements

The identity operation, E, consists of doing nothing to the

molecule. Every molecule has at least this operation and some
have only this operation, so we need it if we are to classify all
molecules according to their symmetry
 Molecular Symmetry
Symmetry operations and elements

In general, an n-fold rotation is a

symmetry operation if the molecule
appears unchanged after rotation by
360º/n. The corresponding symmetry
element is a line, an n-fold rotation
axis, Cn, about which the rotation is
performed.

The trigonal-pyramidal NH3 molecule

has a threefold rotation axis, denoted
C3, but there are now two operations
associated with this axis, one a
clockwise rotation by 120º and the other
an anticlockwise rotation by 120º (C32)
 Molecular Symmetry
Symmetry operations and elements

The square-planar molecule XeF4 has a fourfold C4 axis, but in addition it

also has two pairs of twofold rotation axes that are perpendicular to the
C4 axis: one pair (C2) passes through each trans-FXeF unit and the other pair
(C2) passes through the bisectors of the FXeF angles

By convention, the highest order

rotational axis, which is called the
principal axis, defines the z-axis
(and is typically drawn vertically)
 Molecular Symmetry
Symmetry operations and elements

A plane of reflection (σ) through which an identical copy of the original

molecule is generated

Because the planes are ‘vertical’, in

the sense of containing the
rotational (z) axis of the molecule,
they are labelled with a subscript v,
as in σv and σ′v
 Molecular Symmetry
Symmetry operations and elements

A plane of reflection (σ) through which an identical copy of the original

molecule is generated

The XeF4 molecule has a mirror

plane σh in the plane of the
molecule. The subscript h signifies
that the plane is ‘horizontal’ in the
sense that the vertical principal
rotational axis of the molecule is
perpendicular to it.

This molecule also has two more

sets of two mirror planes that
intersect the fourfold axis (σd) that
bisect t bisects the angle between
two C′2 axes.
 Molecular Symmetry
Symmetry operations and elements

To understand the inversion operation or center of inversion, i, we need

to imagine that each atom is projected in a straight line through a single
point located at the centre of the molecule and then out to an equal
distance on the other side

In an octahedral molecule such as

SF6, with the point at the centre of
the molecule, diametrically
opposite pairs of atoms at the
corners of the octahedron are
interchanged
 Molecular Symmetry
Symmetry operations and elements

An 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

The symmetry element, the improper-

rotation axis, Sn (S4 in the example), is
the corresponding combination of an n-
fold rotational axis and a perpendicular
mirror plane
 Molecular Symmetry
Symmetry operations and elements

An 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

An S1 axis, a rotation through 360º

followed by a reflection in the
perpendicular plane, is equivalent to a
reflection alone, so S1 and σh are the
same; the symbol σh is generally used
rather than S1.

Similarly, an S2 axis, a rotation through

180º followed by a reflection in the
perpendicular plane, is equivalent to an
inversion, i; the symbol i is employed
rather than S2
 Molecular Symmetry
Point Groups
A point group is a group that summarizes all symmetry operations that all
molecules in that category have
 Molecular Symmetry
Point Groups
A point group is a group that summarizes all symmetry operations that all
molecules in that category have
 Molecular Symmetry
Point Groups
The decision tree in can also be used to assign most common point groups
systematically by answering the questions at each decision point. The name of
the point group is normally its Schoenflies symbol (Ih, D4h, C2v, etc)

Molecule

Linear
 Molecular Symmetry
Point Groups
To what point groups do H2O and XeF4 belong?

Molecule

Linear
 Molecular Symmetry
Point Groups
To what point groups do H2O and XeF4 belong?

Molecule

Linear
 Molecular Symmetry
Point Groups

Linear molecules with a centre of

symmetry, such as H2, CO2, and HC≡CH
belong to D∞h.

A molecule that is linear but has no

centre of symmetry, such as HCl or OCS
belongs to D∞v.
 Molecular Symmetry
Point Groups

The Oh and Td point groups are known as cubic groups because they are
closely related to the symmetry of a cube

Shapes having cubic symmetry. (a) The tetrahedron, point group Td. (b) The
octahedron, point group Oh
 Molecular Symmetry
Character Tables
A character table displays all the symmetry elements of the point group
together with a description of how various objects or mathematical
functions transform under the corresponding symmetry operations
 Molecular Symmetry
Character Tables
A character table displays all the symmetry elements of the point group
together with a description of how various objects or mathematical
functions transform under the corresponding symmetry operations

Schoenflies symbol

Irreducible Quadratic functions

representation such as d orbitals
(xy, etc)

Symmetry Functions defined by

species translations or p orbitals
(x,y,z) or rotations (Rx,Ry,Rz)
 Molecular Symmetry
Mulliken Symbols

Degeneracy of the
Characters below Symbols
representation
E Cn i σh C2( ⊥ )/σv

1 1 1 A
1 -1 B
2 2 E
3 3 T

1 Ag Bg Eg Tg
-1 Au Bu Eu Tu
1 A’ B’
-1 A” B”
1 A1 B1
-1 A2 B2
 Molecular Symmetry
Excercise
Identify the symmetry species of the oxygen valence-shell atomic orbitals in
an H2O molecule, which has C2v symmetry
 Molecular Symmetry
Excercise
Identify the symmetry species of the oxygen valence-shell atomic orbitals in
an H2O molecule, which has C2v symmetry

We need to see how the

orbitals behave under
these symmetry operations

The character of the O2py Orbital

under symmetry operations

O O O O
H H H H H H H H

z E C2 σv(x,z) σ’v(y,z)

O O O O
y H H H H H H H H
B2 = +1 -1 -1 +1
x
 Molecular Symmetry
Excercise
Identify the symmetry species of the oxygen valence-shell atomic orbitals in
an H2O molecule, which has C2v symmetry

We need to see how the

orbitals behave under
these symmetry operations

The character of the O2px and

O2 pz orbitals under symmetry
operations

z O2px B1 = +1, -1, +1, -1

O2pz A1 = +1, +1, +1, +1

y

x
 Molecular Symmetry
Excercise
Identify the symmetry species of the oxygen valence-shell atomic orbitals in
an H2O molecule, which has C2v symmetry

An s orbital on the O atom is

unchanged by all four operations,
so its characters are (1,1,1,1) and
thus it has symmetry species A1

z O2s A1 = +1, +1, +1, +1

x
 Molecular Symmetry
Character Table of C3v
A character table displays all the symmetry elements of the point group
together with a description of how various objects or mathematical
functions transform under the corresponding symmetry operations

Schoenflies symbol

Irreducible Quadratic functions

representation such as d orbitals
(xy, etc)

Symmetry Functions defined by

species translations or p orbitals
(x,y,z) or rotations (Rx,Ry,Rz)