Symmetry and Group Theory

Chapter 4
 Symmetry and Group Theory
• The symmetry properties of molecules can be
useful in predicting infrared spectra, describing
the types of orbitals used in bonding, predicting
optical activity, and interpreting electronic
spectra (to name a few).
• The materials in this chapter will be used
extensively throughout the remaining semester.
 Symmetry and Group Theory
• Symmetry element – a geometric entity with
respect to which a symmetry operation is
performed.
• Symmetry operation – a rearrangement of a
body after which it appears unchanged.
Several objects for examples
– Cup, snowflake in the book, your body, and a key
(other objects). For each name the operations and
the elements.
 Types of Molecular Operations
and Elements
• Identity operation (E) – causes no change in the
molecules.
– Every molecule possesses this symmetry.
• Rotation operation or proper rotation (Cn) –
rotation through 360/n about a rotation axis.
– CHCl3 possesses a C3 (clockwise) and a C32
(counterclockwise) rotation angle
– C4H4 (planar) and C6H6 (benzene) – identify the
rotation angles.
 Types of Molecular Operations
and Elements
• Rotation operation or proper rotation (Cn)
– Principal rotation axis – the Cn axis that has the
highest value of n of multiple rotation axes exist.
• Examine CH3Cl, C4H4, and C6H6. Identify other rotation
axes if present.
• C2 passes through several atoms and C2 passes between
the C2 axes and the atoms.
Note: The principal axes is usually chosen as the z-
axis.
 Types of Molecular Operations
and Elements
• Reflection operation () – contains a mirror plane.
– CH3Cl contains multiple mirror planes that contain the
principal axis. These mirror planes are v or d.
• If applicable, the v plane usually intersects several atoms
while d goes between them.
– C4H4 and C6H6 also contain a horizontal plane
perpendicular to the principal axis of rotation. This
plane is called h.
 Types of Molecular Operations
and Elements
• Inversion (i) – each point moves through the center of
the molecule to a position opposite the original position
and as far from the central point as when it started. The
environment at the new point is the same as the
environment at the old point.
– Invert the molecule. If the inversion creates a molecule that
appears identical, the molecule possesses a center of
inversion.
– CH3Cl, C4H4, and CH4 – Determine if the molecules have
inversion symmetry.
 Types of Molecular Operations
and Elements
• Improper rotation or rotation-reflection (Sn) –
requires rotation of 360/n followed by
reflection through a plane perpendicular to the
axis of rotation.
– C4H4 and H3C-CH3 (ethane) Name and identify the
Sn operations performed on ethane.
S2  i (preferred)
S1   (preferred)
Identify the Symmetry Elements
• C4H4
• CH3Cl
• C2H6
• CO
• CO2
It will help to build these molecules with your
model kits (especially in the beginning).
 Point Groups

• The set of symmetry elements for an object/molecule

define a point group. The properties of a particular
group allow the use of group theory. Group theory can
be used to determine the molecular orbitals, vibrations,
and other properties of a molecule.
Website for software:
http://www.emory.edu/CHEMISTRY/pointgrp/index.html
Examine Figure 4-7.
 Finding the Point Group
• Determine whether the molecule belongs to one of the
special cases of low or high symmetry.
– Low symmetry
• C1 (only E), Cs (E and h), and Ci (E and i)
– High symmetry
• Linear with inversion will be Dh; without will be Cv.
• Other point groups; Td, Oh, and Ih
• Find the rotation axis with the highest n.
– This will be the principal axis.
 Finding the Point Group
• Does the molecule have any C2 axes  to the Cn axis?
– If so, the molecule is in the D set of groups.
– If not, the molecule is in the C or S set.
• Does the molecule have a mirror plane (h).
– If so, the molecule is Cnh or Dnh.
– If not, continue with other mirror planes.
• Does the molecule contain any mirror planes that contain the Cn
axis?
– If so, the molecule is Cnv or Dnd.
– If not and in the D group, the molecule is Dn.
– If not and in the C group, continue to next.
 Finding the Point Group
• Is there any S2n axis collinear with the Cn axis?
– If so, the molecule is S2n.
– If not, the molecule is Cn.
• This assignment is very rare.
Vertical planes contain the highest order Cn axis. In the Dnd case,
the planes are dihedral because they are between the C2 axes.
Purely rotation groups of Ih, Oh, and Td are I, O, and T, respectively
(only other symmetry operation is E). These are rare.
The Th point group is derived by adding inversion symmetry to the
T point group. These are rare.
 Determining Point Groups
• HCl • HClBrC-CHClBr
• CO2 • SF6
• PF5 • H2O2
• H3CCH3 • 1,5-dibromonaphthalne
• NH3 • 1,3,5,7-
• CH4 tetrafluorocyclooctatetraene
• CHFClBr • B12H122-
• H2C=CClBr
Properties and Representations of
Groups
• Properties of a group
– Each group must have an identity operation.
– Each group must have an inverse.
– The product of any two group operations must
also be a member of the group.
– The associative property holds.
Understand each property.
 Matrices
• Information about the symmetry aspects of
point groups are summarized in character
tables. Character tables can be thought of as
shorthand versions of matrices that are used to
describe symmetry aspects of molecules.
• A matrix is an ordered array of numbers
represented in columns and rows.
– Illustrate an example.