Symmetry Important - All molecular wave-functions, i.e.

vibrational, rotational, bonding, and electronic, must conform to the requirements imposed by symmetry. Thus, knowledge of symmetry is essential for: 1. Molecular Orbital Theory 2. Spectroscopy, ir, uv-visible, atomic-energy states 3. X-Ray crystal structure determination Symmetry is defined in terms of symmetry elements Point symmetry is represented by Schnflies symbols, which imply the presence of certain symmetry elements. For example, [Ni(CN)4]2- has the symbol D4h, which implied that: a. The molecule is planar b. All NiCN groups are linear c. All C-Ni-C angles are 90 d. All CN groups are equivalent We describe symmetry in terms of symmetry elements. We say that a molecule possesses a certain symmetry element if performance of the symmetry operation required by that symmetry element leaves it indistinguishable from the molecule in its original position. The greater the number of symmetry elements, the higher the symmetry. Symmetry Element 1. 2. 3. Plane Center of symmetry (Inversion center) n-fold axis Symmetry Operation Reflection in plane () Inversion of all atoms through center i One or more rotations about an axis thru 2 360 (Cn) an angle of or n n 2 Rotation through and reflection in n a plane to rotation axis (Sn) Unchanged molecule (E)

4.

n-fold rotation-reflection axis, improper Identity operation

5.

Use flow chart to assign point group symmetry (designated by Schnflies symbols) to a particular molecule. Note that: a. z is conventionally the highest order rotation axis b. elements are qualified by the subscripts v, h, and d as in v, h, and d

The subscript v (for vertical) means the plane contains the highest fold rotation axis Cn. The subscript h (for horizontal) means the plane is perpendicular or horizontal to the highest fold rotation axis Cn. The subscript d (for dihedral) means the plane contains the highest fold rotation axis Cn but bisects the angles between bonds in the horizontal plane. The subscripts and superscripts on other symmetry symbols will be explained later.

Example: Consider BF3

B
F

Symmetry elements E identity C3 three-fold rotation axis 3C2 three two-fold rotation axes 3v subscript v denotes vertical -- mirror plane contains 1h
the highest fold rotation axis C3 subscript h denotes horizontal -- mirror plane to the highest fold rotation axis C3

Point Group Use flow chart to assign point group -- D3h H2O

O
H H

Symmetry Elements E C2 2 v no i Point Group C2v

NH3

N
H H H

Symmetry Elements E C3 3 v no i Point Group C3v

Allene (H2CCCH2)
H H C H H C C

Symmetry Elements C2 2 v no i and no h S4 2 C2' to C2 The C2' axis (see illustration) bisects the angle between the CH2 planes (i.e. v) and is called dihedral axis, denoted by subscript d. Point Group As a result, the point group is D2d.

PF5
F F F F

Symmetry Elements E C3 3 C3 3v 1h no i Point Group D3h

Ferrocene (staggered) Symmetry Elements E S10 C5 5C2 5v i Point Group D5d

Fe

[PtCl4]2Symmetry Elements E C4 4C2 4v 4d 1h i Point Group D4h List the Symmetry Elements and assign the Point group for the following molecules: CH4 [CoF6]3-

Cl Cl

Pt

Cl Cl

2-

Symmetry Elements and Optical Isomerism The usual rule is that a molecule that contains a mirror plane, center of inversion, or improper axis of rotation cannot be optically active. However, since improper axes of rotation include S1 = and S2 i

we can say that a molecule that has no improper axis must be dissymmetric or nonsuperimposable on its mirror image. (For further information, see Chemical Applications of Group Theory 3rd Edition by F. A. Cotton pp. 34-39.)

Identification of Point Groups

Special Groups Linear Tetrahedral Octahedral Icosahedral

Cv, Dh T, Td, Th O, Oh Ih

n-fold roation axis only S2n

no proper axis

symmetry plane only Cs Ci

inversion center only C1

none

S2n

n 2-fold axes

no 2-fold axis

Dnh

horizontal plane

horizontal plane

Cnh

Dnd

n vertical planes

n vertical planes Cnv

Dn

Cn