Vibrating Diatomic Molecule

•-Restoring force α x
•-f α x
•f =-kx
•f is restoring force which is
in direction opposite of
displacement
•k is force constant
•E = k(r-req)2
 Simple Harmonic Oscillator

Oscillatory frequency:osc = Hz where μ =

Allowed vibrational energies for SHO :

Ev = (v + ) hν osc Joule where ν = 0,1,2,3…..

εν = (v + ) osc cm-1 where ν is vibrational Q No

εν+ 1 ν = ( v + 1 + ) osc (v + ) osc = osc cm-1

Morse function: E = Deq [1 – exp{a(req - r)}]2

for ideal case, Schrodinger equation is : E = k (req - r)2

Allowed vibrational energy levels are: εν = (v + ) - xe (v + )2 xe where v = 0,1,2,3…..

For anharmonic oscillator: εν = {1 - xe (v + ) } (v + )
For harmonic oscillator : osc = ) e {1 - xe (v + ) }
Thus anharmonic oscillator behaves like harmonic oscillator, but, with an oscillation frequency
which decreases steadily with invreasing v.
• Case I : v = 0 v = 1 ; Δv = ±1 ,
Considerable Intensity
Δ ε = ε v=1 ‒ ε v=0
= (1 + ) e ‒ xe(1 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 2 xe) cm-1

• Case II : v = 0 v = 2 ; Δv = +2, Small

Intensity
Δ ε = (2 + ) e ‒ xe(2 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 3 xe) cm-1

• Case III : v = 0 v = 3 ; Δv = +2,

Negligible Intensity
Δ ε = (3 + ) e ‒ () e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 4 xe) cm-1
• Case I : v = 0 v = 1 ; Δv = ±1 ,
Considerable Intensity
Δ ε = ε v=1 ‒ ε v=0
= (1 + ) e ‒ xe(1 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 2 xe) cm-1

• Case II : v = 0 v = 2 ; Δv = +2, Small

Intensity
Δ ε = (2 + ) e ‒ xe(2 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 3 xe) cm-1

• Case III : v = 0 v = 3 ; Δv = +2,

Negligible Intensity
Δ ε = (3 + ) e ‒ () e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 4 xe) cm-1
• Case I : v = 0 v = 1 ; Δv = ±1 ,
Considerable Intensity
Δ ε = ε v=1 ‒ ε v=0
= (1 + ) e ‒ xe(1 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 2 xe) cm-1

• Case II : v = 0 v = 2 ; Δv = +2, Small

Intensity
Δ ε = (2 + ) e ‒ xe(2 + )2 e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 3 xe) cm-1

• Case III : v = 0 v = 3 ; Δv = +2,

Negligible Intensity
Δ ε = (3 + ) e ‒ () e ‒ { e ‒ ( )2 xee }
= e (1 ‒ 4 xe) cm-1
Deq r=7
6
5
4
Energy

3
Deq
2 D0
1

0
req
Inter nuclear distance
Deq
Energy

Deq

req
Inter nuclear distance
 osc

osc
E cm-1

osc

osc

Internuclear distance
Simple Harmonic Oscillator
Minimum energy at zero point
Oscillatory frequency:osc = Hz

Where μ =
Allowed vibrational energies for SHO :
Ev = (v + ) hν osc Joule where ν = 0,1,2,3…..

εν = (v + ) osc cm-1 where ν is vibrational Q No

 VIBRATING DIATOMIC MOLECULE

•-Restoring force α x
•-f α x
•f =-kx
•f is restoring force which is
in direction opposite of
displacement
•k is force constant
•E = k(r-req)2
E

req

r
req
r
• -RESTORING FORCE α x
•-f α x
•f =-kx
•f is restoring force which
is in direction opposite of
displacement
•k is force constant
•-Restoring force α x
• -f α x
•f = -kx
•f is restoring force
which is in direction
opposite of displacement
•k is force constant
E

req