Mathematical Group 1. Closure: A, B G AB G 2. Associativity: A, B, C A(BC)= (AB)C 3. Identity: There exists E G such that AE=EA=A for all A G 4.

A G 4. Inverse: A G there exists A-1 G such that AA-1 =A-1A=E

Order of a group: the number of elements it contains

Symmetry of an object point group (symmetry about a point) {E, C2,v,v'} = point group C2v Binary operation: one operation followed by another

Closure: Associativity: Identity: Inverse:

C2v E C2 v

C2 C2 E v v v v

E E C2 v

v v

v v v v E C2 C2 E

C2v E C2 v

C2 C2 E v v v v

E E C2 v

v v

v v v v E C2 C2 E

Rearrangement Theorem: each row and each column in a group multiplication table lists each of the elements once and only once. Proof: suppose AB=AC, i.e. two column entries are identical then: 1 1

A AB = A AC
EB=EC B=C

C2v E C2 v

C2 C2 E v v v v

E E C2 v

v v

v v v v E C2 C2 E

A group is Abelian if AB=BA ( the multiplication is completely commutative). Not all groups are abelian.

v C3 C3 v

Any object (or molecule) may be classified into a point group uniquely determined by its symmetry.

Groups with low symmetry: {E}=C1, Schnflies Symbol/notation {E,} =Cs {E, i} =Ci

ONCl, Cs

F H Cl Cl H

Ci

Groups with a single Cn axis {E, Cn, Cn2, Cn3.Cn n-1} =Cn

H2O2

Groups with a single Cn axis plus a perpendicular h plane: Cnh

N 2O2
2

C2 h

{E , C2 , h , i}

C2 h
Cl

{E , C2 , h , i}
H

C=C
H

Cl

C3 h

{ E , C3 , C , h , S 3 , S }
2 3 5 3

H O

B
H O O H

Groups with a single Cn axis plus n vertical v planes: Cnv

C2 v

H 2O

{E , C 2 , v , v ' }

C3 v NH 3

{ E , C 3 , C , v , v ' , v '' }
2 3

C4 v BrF5

{E , C4 , C2 , C , v , v ' , d , d ' }
3 4

d: dihedral reflection planes (bisects v ) F F Br F F F Square pyramidal

n-gonal pyramidal shape: Cnv

Cv HF
{E , C ,... v ...}

Groups generated by an Sn axis: Sn n odd Cnh n even: Sn

H O

S 2 Ci
H Cl

B
F H O

C3 h
O H

Cl

{E , S 4 , S = C 2 , S }
2 4 3 4

S4
1,3,5,7-tetrafluorocyclooctatetraene F F

F F

Dihedral groups: Groups with a Cn axis plus n perpendicular C2 axes: Dn

C2H6 partly rotated (not staggered, not eclipsed).

D3 = {E , C3 , C , C2 , C , C }
2 3 ' 2 '' 2

Other example:

Ru ( NH 2C2 H 4 NH 2 ) 3
Pt ( NH 2C2 H 4 NH 2 ) 2

Groups with a Cn axis, n C2 axes and a h plane: Dnh

Example: Eclipsed Conformation of Hydrazine, N2H4

D2 h = {E , C2 ( z ), C2 ( y ), C2 ( x), i, xy , yz , xz }

D3h: BF3

5 D3h = {E , C3 , C32 , C2 , C2 ' , C2 ' ' , S3 , S3 , h , v , v ' , v ' '}

D4h: PtCl4

n-gonal prism

Dh: H 2 , BeF2 {E , C ....., v ....., C2 ,.... h , i, S ,....}

Groups with a Cn axis, n C2 axes, and n d planes: Dnd

Symmetry Elements for D3d Point Group (A2X6) C2H6 staggered.

5 D3d = {E , C3 , C32 , C2 , C2 ' , C2 ' ' , i, S 6 , S 6 , d , d ' , d ' '}

Allene

D2 d = {E , C2 , S 4 , S , C2 ' , C2 ' ' , d , d '}

3 4

C C C

staggered regular polygons (n-gonal antiprism)

B2Cl4

Groups with very high symmetry: multiple high fold rotation axes The platonic solids: polyhedra constructed from regular polygons with all vertices and edges equivalent: 5 possibilities only.

icosahedron

dodecahedron None