Lecture 2 Symmetry elements and point groups

Symbol E Cn i Sn Symmetry element whole of space n-fold axis of rotation mirror plane Centre of inversion n-fold axis of improper rotation Symmetry operation Identity Rotation by 360/n Reflection Inversion Rotation by 360/n followed by reflection in plane perpendicular to the rotation axis

When more than one rotation axis is present, the highest order (maxiumum n) is called the principal axis. e.g. BF3 contains a C3 axis and 3 C2 axes perpendicular to the C3 axis. The principal axis in this molecule is C3.

Mirror plans that contain the principal axis are denoted v (vertical) while those that are perpendicular to the principal axis are denoted h (horizontal).

Vertical mirror planes that bisect C2 axes perpendicular to the principal axis are called dihedral planes (d).

Point group classification The symmetry of a molecule can be described by listing all the symmetry elements it possesses. This can be very cumbersome so the symmetry of a molecule is usually described by identifying the point group to which it belongs. A point group is a collection of symmetry elements and is named by a Schnflies point group symbol. The essential symmetry elements defining each point group are described below. Note that some point groups contain additional symmetry elements, but those listed are enough for the unambiguous identification to be made. Molecules which possess no symmetry elements others than E belong to the C1 point group. e.g. CHFClBr Molecules which contain only E and either a mirror plane or a centre of inversion belong to the point groups Cs (e.g. BHFCl) and Ci respectively. Molecules which contain only E and an n-fold axis of rotation belong to the Cn point group The point groups Cnv, Cnh and S2n represent molecules that contain E, only one n-fold axis of rotation and the following: For Cnv n vertical mirror planes v For Cnh a horizontal mirror plane h For S2n an S2n improper axis coincident with the Cn axis e.g. H2O C2v NH3 C3v trans-N2F2 C2h

Molecules that contain more than one rotation axis belong to the dihedral point groups, Dn, Dnd and Dnh. In addition to a principal axis Cn these molecules also contain nC2 axes at right angles to this axis. A molecule that contains only these symmetry elements (E, Cn, nC2) belongs to the point group Dn. For the point group Dnh the molecule contains a horizontal mirror plane (h). For the point group Dnd the molecule additionally contains n vertical mirror planes which bisect the C2 axes (d). e.g. BF3 D3h XeF4 D4h

There are also two high symmetry point groups which linear molecules belong to: Cv E, C axis (molecule unchanged by rotation about any axis), v Dh C axis, v, i, h and C2 perpendicular to principal axis. e.g. CO2 Dh C2HF Cv

Totally symmetrical tetrahedral and octahedral molecules belong to the cubic point groups Td and Oh: Td E, 8C3, 3C2, 6S4, 6d Oh E, 8C3, 6C2, 6C4, 3C2, i, 6S4, 8S6, 3h, 6d There is also a point group Ih which corresponds to a regular icosahedron. Method for identifying the point group of a molecule. As you become familiar with molecule symmetry you will often be able to identify the point group a molecule belongs to immediately. To start with, however, the flow chart shown on the next page provides a step-by-step approach. Examples: Determine the point groups of a) XeF4 b) POCl3 c) trans-CHCl=CHCl d) ClF2

Optical activity and molecular symmetry A molecule is chiral if it cannot be superimposed on its mirror image; each of the mirror images is called an enantiomer. Chiral molecules are optically active as long as they are long-lived to be observed; they rotate the plane of polarised light. The symmetry of a molecule determines its optical activity. Molecules are optically active only if they have no improper rotation axes, Sn. Note that S1 = and S2 = i Point group C2 Can be optically active +
L L Co L L Cl L Cl Cl

Point group D2h Not optically active +

Cl L Co L L

Sample Inorganic Prelims question on molecular shapes and symmetry (a) Predict the structures of the following four molecules and identify those that contain a centre of inversion: POCl3 (b) SO3 BrF4 SF4 [6]

The structure of each of the molecules considered in part (a) contains one or more rotation axes (Cn). For each molecule identify and show by means of a sketch the principal rotation axis present and its order (value of n). [2] Identify the point groups to which the four molecules in (a) belong. [2]

(c)