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Lecture 2 Symmetry elements and point groups

Symbol E Cn σ 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 σv (vertical) while those that are perpendicular to the principal axis are denoted σh (horizontal).

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


nC2) belongs to the point group Dn. Note that some point groups contain additional symmetry elements. The essential symmetry elements defining each point group are described below. Dnd and Dnh. e. H2O C2v NH3 C3v trans-N2F2 C2h Molecules that contain more than one rotation axis belong to the dihedral point groups. Cnh and S2n represent molecules that contain E. For the point group Dnh the molecule contains a horizontal mirror plane (σh). only one n-fold axis of rotation and the following: For Cnv n vertical mirror planes σv For Cnh a horizontal mirror plane σh For S2n an S2n improper axis coincident with the Cn axis e. A point group is a collection of symmetry elements and is named by a Schönflies point group symbol.Point group classification The symmetry of a molecule can be described by listing all the symmetry elements it possesses. For the point group Dnd the molecule additionally contains n vertical mirror planes which bisect the C2 axes (σd). e. A molecule that contains only these symmetry elements (E. Molecules which contain only E and an n-fold axis of rotation belong to the Cn point group The point groups Cnv. Dn. This can be very cumbersome so the symmetry of a molecule is usually described by identifying the point group to which it belongs. BHFCl) and Ci respectively.g. In addition to a principal axis Cn these molecules also contain nC2 axes at right angles to this axis.g.g. but those listed are enough for the unambiguous identification to be made. Cn. BF3 D3h XeF4 D4h 2 . Molecules which possess no symmetry elements others than E belong to the C1 point group. CHFClBr Molecules which contain only E and either a mirror plane or a centre of inversion belong to the point groups Cs (e.g.

σh and ∞C2 perpendicular to principal axis. 6C4. i. 8C3. ∞σv. 6S4. the flow chart shown on the next page provides a step-by-step approach. 3σh. C∞ axis (molecule unchanged by rotation about any axis). i. 8S6.g. 8C3. 3C2. however. ∞σv D∞h C∞ axis. To start with.There are also two high symmetry point groups which linear molecules belong to: C∞v E. 6σd Oh E. As you become familiar with molecule symmetry you will often be able to identify the point group a molecule belongs to immediately. CO2 D∞h C2HF C∞v Totally symmetrical tetrahedral and octahedral molecules belong to the cubic point groups Td and Oh: Td E. 6C2. 3C2. 6S4. 6σd There is also a point group Ih which corresponds to a regular icosahedron. Examples: Determine the point groups of a) XeF4 b) POCl3 c) trans-CHCl=CHCl d) ClF2– 3 . e. Method for identifying the point group of a molecule.

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The symmetry of a molecule determines its optical activity. Molecules are optically active only if they have no improper rotation axes.Optical activity and molecular symmetry A molecule is chiral if it cannot be superimposed on its mirror image. [2] Identify the point groups to which the four molecules in (a) belong. they rotate the plane of polarised light. Chiral molecules are optically active as long as they are long-lived to be observed. each of the mirror images is called an enantiomer. Sn. For each molecule identify and show by means of a sketch the principal rotation axis present and its order (value of n). Note that S1 = σ 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). [2] (c) 5 .