# 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, σ 3. Inversion through a central point , I 4. Improper rotation or a rotary reflection, S 5. The identity, E

C64 ≡ C32 3 C 6 → C 6 . C 6 → C6 .1. C 66 → E . C 62 → C 3 . C3 An operation 3 C3 ≡ E . C 6 → C2 SO. C34 ≡ C3 k Cn eg. WE HAVE 5 5 C 64 → C 32 . C6 ≡ C2 . C32 . PROPER ROTATION : Cn (rotation by an angle 2π/n) 1 3 C3 . by an angle 2πk/n ≡ alternative way if n/k is an integer 3 C62 ≡ C3 .

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C −k n ≡C Principle Axis ≡ Cn axis having maximum n 2. C32 ≡ C3−1 and C3 ≡ C3−2 n−k n In general. Reflection : mirror-plane should pass through the molecule & σv σh σd σ2 ≡ E Vertical mirror plane (along principle axis) Horizontal mirror plane (parpendicular to principle axis Dihedral plane – bisecting the angle between two C2 axes .Also.

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Inversion : Every atom (except central atom if any) in the molecule must occur in pairs i2 ≡ E .3.

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4. Improper Rotation OR Rotary-reflection .

neither the Cn axis nor the mirror plane need be symmetry elements themselves . This operation is defined as the two procedures together. After just the rotation the structure may be completely different from the start point.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. The molecule has an Sn axis of symmetry if the combined rotation–reflection gives a result indistinguishable from the start point.

S = C3 . both σh and Cn must exist independently.S = S . S = S . S = S . S = C . S = i 2 6 3 6 S = C . then only Also. S =σ 2 5 2 5 3 5 3 5 4 5 4 5 5 5 S = C5. i ≡ S2 σ ≡ S1 about any axis through the centre about an axis perpendicular to the mirror plane S 6 = S 6 .even n Sn ≡E because n Cn ≡ E & σ evenn ≡ E Neither Cn nor σ need to exist separately. then Sn must exist For n . If both exist. S = E 6 5 7 5 7 5 8 5 3 5 9 5 9 5 10 5 .S = E 4 6 2 3 5 6 5 6 6 6 S5 = S5. S = S .Improper Rotation OR Rotary-reflection For n .odd n Sn ≡σh and because σ odd − n ≡ σ 2n Sn ≡E n +1 n +1 Sn ≡ Cn ≡ Cn So. S = C . S = C .

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 .Also.

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QP ≠ PQ. Note that(PQ)(Q-1P-1) = P(QQ-1)P-1 = PEP-1 = PP-1 = E Therefore. 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. then Q & P are said to commute E & i will commute with all other operations: RE = ER = R Also. Thus R-1R = RR-1 = E.Products of symmetry operations P = Q equivalence of two operators The index notation (successive repetition) follows the usual algebraic rules for products. Therefore. If QP=PQ. Thus. (PQ)-1 = Q-1P-1 . σ & i are their own inverse. 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. TR = T(QP) = (TQ)P =TQP (Associative) .

Find all the symmetry elements of the following molecules Find all the symmetry elements of the following molecules .