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Chem 353 Fall 2008

Symmetry Notes

Symmetry The correspondence in size, form, and arrangement of parts on opposite sides of a plane, line, or point Regularity in form or arrangement in terms of like, reciprocal, or corresponding parts A property of a physical system that allows the system to remain unchanged by a specific physical or mathematical transformation, such as translation or rotation Examples of the applications of symmetry in chemistry can be found in spectroscopy: electronic vibrational NMR optical activity polarity bonding descriptions

We will discuss the formal aspects of symmetry in molecules. This will equip us with a tool to develop molecular orbital descriptions of bonding in molecules.

Symmetry Elements and Operations: Two distinct but interrelated things! SYMMETRY ELEMENT - A geometric entity (point, line, plane) SYMMETRY OPERATION - Movement of an object about a symmetry element such that the before and after positions and orientations of the object are indistinguishable. Fundamental types of symmetry Element 1. Identity 2. Inversion centre/ centre of symmetry 3. Mirror plane 4. Proper rotation axis Operation Do nothing Invert all parts through the point Reflect in the plane Rotate about the axis by (360/n)o Rotate by m(360/n)o Cn Cnm Sn Symbol E i

5. Improper rotation axis

Rotate by (360/n)o and then reflect in a plane perpendicular to the axis.

Chem 353 Fall 2008

Symmetry Notes

Example: NH3

symmetry elements? symmetry operations? H

N H

H H

N H H

Example: PtCl42Symmetry elements? Operations? Cl Cl Cl Pt Cl Cl Cl Pt Cl Cl

The number and kinds of symmetry elements/operations found in molecules come in special combinations or groups. POINT GROUPS: A complete set of symmetry elements/operations for a given molecular shape. Point groups are designated by a simple notation which indicates precisely all of the elements/operations present: SCHNFLIES symbols: A code for the symmetry present in a particular molecule. We will examine the various classes of point group symmetry by starting with molecules having little or no symmetry and gradually working up to higher (more) symmetry groups.

Chem 353 Fall 2008

Symmetry Notes

Low symmetry point groups C1 no symmetry (but does possess E) e.g. CHFClBr

Cs

mirror plane only

e.g.

SO2FBr, CH2FCl

Ci

inversion centre only

e.g. staggered HBrClC-CClHBr

Purely Rotational Point Groups Cn one rotational axis (+ Cn2, Cn3..Cnn-1)

Chem 353 Fall 2008

Symmetry Notes

if we add a mirror plane parallel to Cn (vertical mirror plane, v), the combination generates a total of n vs Cnv e.g. NH3, BrF5, CH3CN

if instead of adding a vertical mirror plane we combine Cn with a mirror plane perpendicular (horizontal, h): Cnh e.g. B(OH)3

if we combine a Cn with an S2n axis coincident with the Cn axis, the result is S2n e.g. 1,3,5,7-tetramethyl-cyclooctatetraene
CH3

CH3
CH3
H3C

H3C
CH3

H3C CH3

Chem 353 Fall 2008

Symmetry Notes

A number of point groups have more than one rotational axis -most often one is desginated the primary axis and the others are all C2 axes perpendicular to the primary axes. If no other elements are present, Dn e.g. gauche ethane

vertical mirror planes may be added to Dn such that they bisect the C2 axes - as such they are called dihedral mirror planes d Dnd has a Cn, n C2s, n ds, and S2n (coincident to the Cn) and i (if n=odd). e.g. allene

Chem 353 Fall 2008

Symmetry Notes

if a horizontal mirror plane (h) is added, the result is Dnh Cn, nC2, h, nv/d, Sn, i (n=even) e.g. BF3, benzene

Linear Point Groups contain a C axis concident with the molecular axis Cv e.g. HCl, HCN

if the molecule also has a h Dh e.g. H2, HCCH, CO2

Chem 353 Fall 2008

Symmetry Notes

High symmetry groups - these contain lots of symmetry, but are often intuitively obvious. Td: T: has 4 C3 axes, 3 C2, 3 S4, and 6 d e.g. CH4

has all the rotational axes found in Td but no mirror planes.

O h: O:

4C3, 6C2, 3C4, i , 3S4, 4S6, 3h, 6d rotational symmetry only from Oh

e.g. Cr(CO)6

I h:

A total of 120 symmetry elements - six C5 axes e.g. B12H122- , C60

Chem 353 Fall 2008

Symmetry Notes

How to determine molecular point groups: A foolproof step-by-step guide yes

no Is there one Cn axis? yes yes Is there more than one Cn (n>2)? no Is there a C2 perpendicular to the first Cn? no Is there a h? no Is there a v? no Is there an S2n? no yes yes yes yes no

C1 , Cs , Ci

Td , T , Oh , O , Ih

Cnh

Is there a h? no

yes

Is the molecule linear?

v,

Dnh

Cnv

Is there a v? no

yes

Dnd

S2n

Dn

Cn
NOTE: you will need to learn to determine point groups without this chart!

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