Part II: Symmetry Operations and Point Groups

C734b

C734b Symmetry Operations and Point groups

Definitions 1.- symmetry operations: leave a set of objects in indistinguishable configurations 1.said to be equivalent -The identity operator, E is the do nothing operator. Therefore, its final configuration is not distinguishable from the initial one, but identical with it. 2.- symmetry element: a geometrical entity (line, plane or point) with respect to 2.which one or more symmetry operations may be carried out. Four kinds of symmetry elements for molecular symmetry 1.) Plane operation = reflection in the plane 2.) Centre of symmetry or inversion centre: operation = inversion of all atoms through the centre 3.) Proper axis operation = one or more rotations about the axis

4.) Improper axis operation = one or more of the sequence rotation about the axis followed by reflection in a plane perpendicular () to the rotation axis.
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1. Symmetry Plane and Reflection

A plane must pass through a body, not be outside. Symbol = . The same symbol is used for the operation of reflecting through a plane m as an operation means carry out the reflection in a plane normal to m.

Take a point {e1, e2, e3} along

(x, y, z )

x{e1, e2, e3} = {-e1, e2, e3}

e1 , e 2 , e 3

Often the plane itself is specified rather than the normal.

x = yz means reflect in a plane containing the y- and z-, usually called the yz olane

C734b Symmetry Operations and Point groups

-atoms lying in a plane is a special case since reflection through a plane doesnt move the atoms. Consequently all planar molecules have at least one plane of symmetry molecular plane Note: produces an equivalent configuration. 2 = produces an identical configuration with the original.

2 = E n = E for n even; n = 2, 4, 6, n = for n odd; n = 3, 5, 7,

C734b Symmetry Operations and Point groups

Some molecules have no -planes:

S F

O Cl

Linear molecules have an infinite number of planes containing the bond axis.

Many molecules have a number of planes which lie somewhere between these two extremes: Example: H2O

O
H

2 planes; 1 molecular plane + the other bisecting the H-O-H group

H
5

C734b Symmetry Operations and Point groups

Example: NH3

N H H

3 planes containing on N-H bond and bisecting opposite HNH group

Example: BCl3

Cl

Cl B
Cl

4 planes; I molecular plane + 3 containing a B-Cl bond and bisecting the opposite Cl-B-Cl group

Example: [AuCl4]square planar

Cl Cl

Au

Cl Cl

5 planes; 1 molecular plane + 4 planes; 2 containing Cl-Au-Cl + 2 bisecting the Cl-Au-Cl groups.

C734b Symmetry Operations and Point groups

Tetrahedral molecules like CH4 have 6 planes.

H C H H

Octahedral molecules like SF6 have 9 planes in total

F F S F F
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F F

2.) Inversion Centre

-Symbol = i - operation on a point {e1, e2, e3}
z

i{e1, e2, e3} = {-e1, -e2, -e3}

z

i e3 -e2 e1 x e2 y -e3 x y -e1

C734b Symmetry Operations and Point groups

-If an atom exists at the inversion centre it is the only atom which will not move upon inversion. -All other atoms occur in pairs which are twins. This means no inversion centre for molecules containing an odd number of more than one species of atoms.

i2 = ii = E

in = E in = i

n even n odd

C734b Symmetry Operations and Point groups

Example: 2 1

Cl Cl
3

Au

Cl Cl
4

Cl Cl
1
-

Au

Cl Cl
2

but
H

or
H

H C H H

have no inversion centre even though in the methane case the number of Hs is even
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3. Proper Axes and Proper Rotations

- A proper rotation or simply rotation is effected by an operator R(,n) which means carry out a rotation with respect to a fixed axis through an angle described by some unit vector n. For example: R(/4, x){e1, e2, e3} = {e1, e2, e3}
z z

R(/4, x) e3 e2 y e1' x e3'

45

e2'
45
o

e1 x

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Take the following as the convention: a rotation is positive if looking down axis of rotation the rotation appears to be counterclockwise. More common symbol for rotation operator is Cn where n is the order of the axis.

Cn means carry out a rotation through an angle of = 2/n R(/4) C8

R(/2) = C4

R() = C2

etc.

C2 is also called a binary rotation.

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Product of symmetry operators means: carry out the operation successively beginning with the one on the right.

C4C4 = C42 = C2 = R(, n)

(Cn)k = Cnk = R(, n); = 2k/n Cn-k = R(-, n); = -2k/n CnkCn-k = Cnk+(-k) = Cn0 E Cn-k is the inverse of Cnk

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Example:

C31 C3

1 I

= rotation by 2/3 = 120o

2 II

C3 axis is perpendicular to the plane of the equilateral triangle. 2 C3C3 = C32 1

= rotation by 4/3 = 240o

C734b Symmetry Operations and Point groups

3 III

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But 2 1 C3-1

= rotation by -2/3 = -120o C32 = C3-1

III

2 1

2 C3
3

= rotation by 2 = 360o C33 = E

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What about C34? 3 C34 = C3C3C3C3

3 C34 = C3

II

only C3, C32, E are separate and distinct operations

Similar arguments can be applied to any proper axis of order n

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Example:

C6: C6; C62 C3 C63 C2 C64 C6-2 C3-1 C65 C6-1 C66 E

Note: for Cn n odd the existence of one C2 axis perpendicular to or containing Cn implies n-1 more separate (that is, distinct) C2 axes or planes 1 C5 axis coming out of the page 2
H

5
H

4
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* When > one symmetry axis exist, the one with the largest value of n PRINCIPLE AXIS Things are a bit more subtle for Cn, n even Take for example C4 axis: C2(1) 2 1 C2(2)

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C2(2) 1 C4 4 C2(1)

2 i.e.; C2(1) C2(2); C2(2) C2(1)

C2(1) 4 C4 Total = C42 = C2 i.e.; C2(1) C2(1); C2(2) C2(2) 1 2

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3 C2(2)

C734b Symmetry Operations and Point groups

C2(1) 2 C4 1 C2(2)

Total C43 = C4-1 3 i.e.; C2(1) C2(2); C2(2) C2(1) 4

Conclusion: C2(1) and C2(2) are not distinct Conclusion: a Cn axis, n even, may be accompanied by n/2 sets of 2 C2 axes

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10

b2

a2

b1

a1

4 C2 axes: (a1, a2) and (b1, b2).

Cn rotational groups are Abelian

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4. Improper Axes and Improper Rotations

Accurate definitions: Improper rotation is a proper rotation R(, n) followed by inversion iR(, n) Rotoreflection is a proper reflection R(, n) followed by reflection in a plane normal to the axis of rotation, h Called Sn = hR(, n) = 2/n

Cotton and many other books for chemists call Sn an improper rotation, and we will too.

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Example: staggered ethane (C3 axis but no C6 axis) 1 1 3 2 C6 6 4 6 5 3 4 5 3 1 2 2 h 6 5

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Note: 1 6 3 2 h 6 4 3 5 5 1 1 2 3 Sn = hCn or Cnh 2 4 C6 6 5

The order is irrelevant.

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Clear if Cn exists and h exists Sn must exist. HOWEVER: Sn can exist if Cn and h do not. The example above for staggered ethane is such a case.

The element Sn generates operations Sn, Sn2, Sn3, However the set of operations generated are different depending if n is even or odd.

n even {Sn, Sn2, Sn3, , Snn} But hn = E and Cnn = E {hCn, h2Cn2, h3Cn3, , hnCnn}

Snn = E

and therefore: Snn+1 = Sn, Snn+2 = Sn2, etc, and Snm = Cnm if m is even.

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Therefore for S6, operations are: S6 S62 C62 C3 S63 S2 i S64 C64 C32 S65 S6-1 S66 E

Conclusion: the existence of an Sn axis requires the existence of a Cn/2 axis. Sn groups, n even, are Abelian.

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n odd Consider Snn = hnCnn =hE = h

h must exist as an element in its own right, as must Cn.

Consider as an example an S5 axis. This generates the following operations:

S51 = hC5 S52 = h2C52 C52 S53 = h3C53 hC53 S54 = h4C54 C54 S55 = h5C55 h Its easy to show that S511 = S5 Sn groups, n odd, are not Abelian

S56 = h6C56 C5 S57 = h7C57 hC52 S58 = h8C58 C53 S59 = h9C59 hC54 S510 = h10C510 E The element Sn, n odd, generates 2n distinct operations
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C734b Symmetry Operations and Point groups

a) A body or molecule for which the only symmetry operator is E has no symmetry at all. However, E is equivalent to a rotation through an angle = 0 about an arbitrary axis. It is not customary to include C1 in a list of symmetry elements except when the only symmetry operator is the identity E. b) = 2/n; n is a unit vector along the axis of rotation.
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Products of Symmetry Operators

-Symmetry operators are conveniently represented by means of a stereogram or stereographic projection. Start with a circle which is a projection of the unit sphere in configuration space (usually the xy plane). Take x to be parallel with the top of the page.

A point above the plane (+z-direction) is represented by a small filled circle. A point below the plane (-z-direction) is represented by a larger open circle.

A general point transformed by a point symmetry operation is marked by an E.

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For improper axes the same geometrical symbols are used but are not filled in.
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C734b Symmetry Operations and Point groups

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Example: Show that S+(,z) = iR-(-, z)

Example: Prove iC2z = z

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The complete set of point-symmetry operators including E that are generated from the operators {R1, R2, } that are associated with the symmetry elements {C1, i, Cn, Sn, } by forming all possible products like R2R1 satisfy the necessary group properties:

1) 2) 3) 4)

Closure Contains E Satisfies associativity Each element has an inverse

Such groups of point symmetry operators are called Point Groups

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Example: construct a multiplication table for the S4 point group having the set of elements: S4 = {E, S4+, S42 = C2, S4-}

S4 E
+ S4 C2 S4

E E
+ S4 C2 S4

+ S4 + S4

C2 C2

S4 S4

Complete row 2 using stereograms: S4+S4+, C2S4+, S4-S4+ (column x row)

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Complete Table

S4 E
+ S4 C2 S4

E E
+ S4 C2 S4

+ S4 + S4

C2 C2
S4 E + S4

S4 S4

C2 S4 E

E + S4 C2

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Another example: an equilateral triangle

Choose C3 axis along z The set of distinct operators are G = (E, C3+, C3-, A, B, C} y b

a c

Blue lines denote symmetry planes.

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b Let 1 = c a c b E1 = c a C3+1 = b c C3-1= a b = 3 C1 = c

C734b Symmetry Operations and Point groups 39

= 1

A1 = b b

= 4

= 2

B1 = a a

= 5

= 6

Typical binary products: c C3+C3+1 = C3+2 a b C3+C3-1 = C3+3 c a C3+A1 = C3+4 c b AC3+1 = C3+2 a Note: i) A and C3+ do not commute c B1 b C1 a E1 b C3-1

etc.

C3+C3+ = C3-

C3+C3- = E

C3+A = C

AC3+ = B

ii) Labels move, not the symmetry elements

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C734b Symmetry Operations and Point groups

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Can complete these binary products to construct the multiplication table for G Multiplication Table for the set G = {E, C3+, C3-, A, B, C}

G E C3+ C3

E E C3+ C3

C3+ C3+ C3 E

C3 A C3 A E C C3+

B B A C

C C B A

A A B C E C3+ C3 B B C A C3 E C3+ C C A B C3+ C3 E

C734b Symmetry Operations and Point groups 41

Symmetry Point Groups (Schnflies notation) (Sch One symmetry element

1.) No symmetry: C1 {E exists} order = 1

2.) sole element is a plane:

Cs

{, 2 = E}

order = 2

3.) sole element is an inversion centre:

Ci

{i, i2 = E}

order = 2

4.) Only element is a proper axis of order n: {Cn1, Cn2, , Cnn = E} order = n

Cn These are Abelian cyclic groups.

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5.) Only element is an improper axis of order n.

Two cases: a) n even Note: S2 = i. Symbol: Sn {E, Sn, Cn/2, Sn3, , Snn-1 order = n

S2 = Ci

b) n odd

order = 2n including h and operations generated by Cn axis. Cnh

Symbol:

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Two or more symmetry elements

Need to consider (1) the addition of different symmetry elements to a Cn axis and (2) addition of symmetry planes to a Cn axis and nC2 axes perpendicular to it.

To define symbols, consider the principle axis to be vertical. vertical

Symmetry plane perpendicular to Cn will be a horizontal plane h

There are 2 types of vertical planes (containing Cn) If all are equivalent

v ( v vertical)

There may be 2different sets (or classes) one set = v; the other set = d (d = dihedral)
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adding h to Cn Cnh ( Sn; n odd) adding v to Cn: n odd nv planes n even n/2 v planes and n/2 d planes

See previous discussion regarding C4 axis. Note: the d set bisect the dihedral angle between members of the v set.

Distinction is arbitrary:

Cnv

point group.

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Next: add h to Cn with n C2 axes

Dnh

point group

(D for dihedral groups)

Note: hv = C2. Therefore, need only find existence of Cn, h, and vs to establish Dnh group. By convention however, simultaneous existence of Cn, n C2s, and h used as criterion. Next: add ds to Cn and n C2 axes. d vertical planes which bisect the angles between adjacent vertical planes

Dnd

point group
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Special Cases
1.) Linear molecules: each molecule is its own axis of symmetry. no h: h exists: order =

Cv Dh

point group

point group

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2.) Symmetries with > 1 high-order axis higha) tetrahedron Elements = {E, 8C3, 3C2, 6S4, 6d}

Td

point group

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b) Octahedron (Cubic Group) Group elements: {E, 8C3, 6C2, 6C4, 3C2 (= C42), i, 6S4, 8S6, 3h, 6d}

Oh

point group

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c) Dodecahedron and icosahedron

Group elements: {E, 12C5, 12C52, 20C3, 15C2, i, 12S10, 12S103, 20S6, 15}

Ih

point group

(or Y point group)

icosahedron

dodecahedron

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There are 4 other point groups: T, Th, O, I which are not as important for molecules.
C734b Symmetry Operations and Point groups 51

A systematic method for identifying point groups of any molecule

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