Expression for Energy of a Harmonic Oscillator
Recursion relation obtained for Harmonic oscillator
For the series to break off after a finite number of terms, the coefficient of Cn must become
zero for some value of n, (say n = v)
v 0
v
Substituting for α and rearranging ; v
v v = 0, 1, 2, 3......
3
v
2
1 Equally spaced energy levels v
0
PE=E, KE=0
E
KE
E
PE
-x -a 0 a x
-x 0 a x classically allowed –a ≤ x ≤ a
classically forbidden –a < x, x>a
Classical turning points
Vibration of a molecule
For a diatomic molecule, the nuclear Schrödinger equation is a two particle equation
When PE of a two particle system depends only on the distance between the particle, the
energy of the system is the sum of the KE of the translational motion of the hypothetical
system whose mass is μ=m1m2/(m1+m2) through space and the energy of the internal motion
of the particles relative to each other.
The Schrödinger equation for the vibration of a diatomic molecule has a kinetic energy operator
for the hypothetical particle of mass μ and PE term U(R). The minimum of the potential energy
curve occurs at the equilibrium distance Re between the nuclei
The Harmonic oscillator force constant
R=Re
The vibration of real molecules do not follow the above model
Vibrations of molecules: More details
All molecules are not IR active Condition apply:
Gross Selection Rule: Change in dipole moment during vibration H2: Not IR active
HCl: IR active
O=C=O ?????
Specific Selection rule : Δv = +1 v is the vibrational quantum number
-
V=3
V=2
V=1 X
V=0
The frequency of vibration is given by ν=
Frequency of vibration is generally expressed in wave numbers (cm-1)
-ν = ν/c
Frequencies corresponding to some of the functional groups
C=O 1680-1730 cm-1
C C 1100-1200 cm-1
C=C 1620-1680 cm-1
_
C=C 2100-2250cm-1
O-H 3600 cm-1
~3360 cm-1
- O-H ....................O=C-
Strength of bond is decreased
due to hydrogen bonding and ν- is decreased
Real system (molecules)
Re
Harmonic Oscillator E = (v + ½) hν
Anharmonic Oscillator
E = (v + ½) hν - (v + ½ )2 hνxe
Modes of vibrations N is the number of atoms
3N- 5 modes for linear molecules 3N- 6 modes for non-linear molecules
H2 linear H2O non-linear
3x2–5 =1 3x3–6 =3
H H
Symmetric stretch
3657cm-1 3756cm-1 1595 cm-1
CO2 vibrational modes
1337cm-1
667cm-1
2349 cm-1
Fundamental, combination, overtones and Fermi Resonance
The fundamental modes of vibrations ν1, ν2, ν3, ν4
Combinations bands of vibrations ν1+ ν2 ν2 + ν4 , ν1- ν2, ν3 - ν2 etc.
The fundamental ν1, ν2, etc.
Overtones of vibrational modes 2ν1, 2ν2 etc. ( First overtones)
3ν1, 3ν2 etc. ( Second overtones)
.
.
etc.
Fermi resonance: When the fundamental of one vibrational mode is close to ovetone of other
fundamental vibration, vibrational bands appear in the IR spectrum on both sides of them.
The intensity of such Fermi resonance bands will be more than that of the overtone bands but
less than that of the fundamental
Consider the case, ν1 ~ 2ν2
vibrational bands in IR spectrum appear at ν1 + x and 2 ν2 - x where x ~ ν1 -2 ν2 If 2ν2 < ν1
ν1 - x and 2 ν2 + x
If ν1 < 2ν2
For light diatomic molecules,
V=2
V = 0 is mostly populated V=1
V=0
For heavy diatomic molecules,
significant population in the first few excited states
v = 1, 2 etc.
V=2 V=2
V=1 V=1
V=0 V=0
V = 0 is mostly populated
V=2
V=1
V=0
Higher Temperatures
V=2 V=2
V=1 V=1
V=0 V=0
HOT BANDS
The probability of transition from state ‘n’ to state ‘m’ is expressed in terms of transition dipole moment
allowed
The dipole moment changes slightly as the molecule vibrates.
Both amplitude of vibration and dipole moment are functions of time
The oscillating dipole moment μx can be expanded as a Taylor series
Substituting for the wave functions and the dipole moment in the equation for TDM
0 0 only if
the integrand is an odd function
?
even odd
odd
≠ 0 ; if the excited state is an odd function
0
0=
Odd function
Even function
odd function
X ≠ 0 ; for Δv = ±1
Even function -x 0 +x
If ǂ 0 Transition is allowed
It is not the permanent dipole moment,
but the change in dipole moment during vibration is the deciding factor!!!
(Gross Selection rule)
Only Quantum Mechanics!!!!
