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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
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
1 3 C3 , C32 , C3
An operation
3 C3 E ; C34 C3
k Cn
eg.
by an angle 2k/n
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
v h d
2 E
Vertical mirror plane (along principle axis) Horizontal mirror plane (parpendicular to principle axis
i2 E
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
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
Also,
i S2
S1
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
k k+ p Cnp Cn = Cn
QP=R
R is some other single operator
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
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