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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
Symmetry Notes
Example: NH3
N H
H H
N H H
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.
Symmetry Notes
Low symmetry point groups C1 no symmetry (but does possess E) e.g. CHFClBr
Cs
e.g.
SO2FBr, CH2FCl
Ci
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
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
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
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
O h: O:
4C3, 6C2, 3C4, i , 3S4, 4S6, 3h, 6d rotational symmetry only from Oh
e.g. Cr(CO)6
I h:
Symmetry Notes
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
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!