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LASER & SPECTROSCOPY - I

M. Sc. (PHYSICS) III SEMESTER

A. G. VEDESHWAR
LECTURE- 1

MOLECULAR SYMMETRY & GROUP THEORY SYMMETRY OPERATIONS Movement of the system, when completed, brings every point either to its original position or to an indistinguishable position in its original orientation

For an isolated molecule, there are five distinct symmetry operations.

1. Rotation about an axis, C 2. Reflection in a mirror-plane, 3. Inversion through a central point , I 4. Improper rotation or a rotary reflection, S 5. The identity, E

1. PROPER ROTATION : Cn

(rotation by an angle 2/n)

1 3 C3 , C32 , C3
An operation

3 C3 E ; C34 C3

k Cn
eg.

by an angle 2k/n

alternative way if n/k is an integer

3 C62 C3 ; C6 C2 ; C64 C32


3 C 6 C 6 ; C 62 C 3 ; C 6 C2

SO, WE HAVE

5 5 C 64 C 32 ; C 6 C6 ; C 66 E

Also,

C32 C31

and

C3 C32
nk n

In general,

k n

Principle Axis

Cn

axis having maximum n

2. Reflection : mirror-plane should pass through the molecule &

v h d

2 E

Vertical mirror plane (along principle axis) Horizontal mirror plane (parpendicular to principle axis

Dihedral plane bisecting the angle between two C2 axes

3. Inversion : Every atom (except central atom if any) in the molecule


must occur in pairs

i2 E

4. Improper Rotation OR Rotary-reflection

An improper rotation Sn is actually a combination of two operations: a rotation about a Cn axis and then a reflection through a plane which is horizontal with respect to the axis. This operation is defined as the two procedures together. The molecule has an Sn axis of symmetry if the combined rotationreflection gives a result indistinguishable from the start point. After just the rotation the structure may be completely different from the start point; neither the Cn axis nor the mirror plane need be symmetry elements themselves

Improper Rotation OR Rotary-reflection


For n - even

n Sn E

because

n Cn E & evenn E

Neither Cn nor need to exist separately. If both exist, then Sn must exist
For n - odd

n Sn h
and

because

odd n
2n Sn E

n +1 n +1 Sn Cn Cn

So, both h and Cn must exist independently, then only

Also,

i S2
S1

about any axis through the centre

about an axis perpendicular to the mirror plane

S 6 = S 6 ; S = C3 ; S = i
2 6 3 6

S = C ;S = S ;S = E
4 6 2 3 5 6 5 6 6 6

S5 = S5; S = C ; S = S ; S = C ; S =
2 5 2 5 3 5 3 5 4 5 4 5 5 5

S = C5; S = S ; S = C ; S = S ; S = E
6 5 7 5 7 5 8 5 3 5 9 5 9 5 10 5

Also,

S = S &S = S
5 6 3 5
In general,

1 6

7 5

S =S
k n
k n

k n n
k 2n n

For n = even

S =S

For n = odd

Products of symmetry operations


P = Q equivalence of two operators The index notation (successive repetition) follows the usual algebraic rules for products. Thus,

k k+ p Cnp Cn = Cn
QP=R
R is some other single operator

Product notation: effect of operator P followed by that of Q as

In general, QP PQ. If QP=PQ, then Q & P are said to commute E & i will commute with all other operations: RE = ER = R

Also, TR = T(QP) = (TQ)P =TQP (Associative) ; where T is another operator We have

k k Cn Cn = E

Such that SR = RS = E

We say S is the inverse operator to R and S = R-1 or R = S-1, Thus R-1R = RR-1 = E. Therefore, & i are their own inverse. Note that(PQ)(Q-1P-1) = P(QQ-1)P-1 = PEP-1 = PP-1 = E Therefore, (PQ)-1 = Q-1P-1

Find all the symmetry elements of the following molecules

Find all the symmetry elements of the following molecules

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