Chapter 5.

Harmonic Oscillator & Rigid Rotor

- Harmonic Oscillator (HO): Model for Vibrations Hookes law (force), harmonic potential, Reduced mass, center-of-mass Anharmonic potential, Morse potential Energy levels and HO wavefunctions Selection rules for vibrational transition - Rigid Rotor: Model for Rotations Energy levels Wavefunction: spherical harmonics Selection rules for rotational transition

Rigid Rotor: Simple Model for Rotations

moment of inertia
r2 m2 r r1

Center of mass

m1

COM fixed

Use of spherical coordinate

nuc = H vib + H rot ; nuc ( r , , ) = ( r )Y ( , ) H rotY ( , ) = ErotY ( , ) H

rotY ( , ) = H

Harmonic Oscillator: Classical View of Vibrations

Hookes Law & Waveform
l0

&( 0) = 0 x ( 0 ) = A, x
l

kA2 E = K +V = 2
+A
E = K(x) + V (x) V (x) K(x)

x(t)
A

T=

; =

+A

Harmonic Oscillator: Diatomic Molecules

m1 m2

x1

x2

- Center of mass (COM) is fixed in space COM coordinate: - Vibrational motion occurs by action of reduced mass x = x2 x1 l0

1 1 d 2 x2 d 2 x1 k k d2x k 2 = + x x 2 = k x= x 2 dt dt m2 m1 dt m2 m1 d2x 2 + kx = 0 = reduced m ass; = dt k

Harmonic Oscillator Approximation & Anharmonicity

HO

Energy

Real
l0

10 8

Morse Potential

anharmonicity (mechanical)

V ( l ) / 10 1 9 J

6 4 2 0 0 100 200 300 400

V ( l ) = D (1 e
2

( l l0 ) 2

k = 2 D , = ?
l / pm

QM Harmonic Oscillator: Eigenvalues

2 2 d h 1 2 1 1 = H kx a a v h h + = + = + + 2 dx 2 2 2 2

lowering op a 2h raising op a + 2h

1/ 2

ip x +

1/ 2

ip h d , x p = i dx

v=4 v=3

Quantum number : = 0, 1, 2,...

Vibrational frequency:

Energy

v=2 v=1 v= 0

Use of ladder operators: P5-39,40, PS4

QM Harmonic Oscillator: Vibrational frequencies

Selection rule : = 1

570

Harmonic Oscillator Wavefunctions

Hermite polynomials Normalization factor

v
3

3 ( x ) 2 ( x ) 1 ( x ) 0 ( x )

3 ( x )

7 h 2 5 h 2 3 h 2

2 ( x ) 1 ( x ) 0 ( x )

1 h 2

x (a)

x (b)

HO Wavefunctions: Hermite Polynomials

H ( ) = even if = even; odd if = odd

=0

Rigid Rotor: Rotational Spectrum

Eigenvalue: Eigenfunction:

= BJ ( J + 1 )
Y ( , ) = YJM J ( , ) " Spherical Harmonics" = JM J ( ) M J ( ) ( in Chapter 6 ) JM J ( ) = N JM J PJ|M J | (cos ), M J ( ) = 1 iM J e 2 associated Legendre polynomials

J 4

Rotational energy levels

~ E = 8B 3 ~ E = 6B 2 ~ E = 4B 1 ~ E = 2B 0

Selection rule: E

Hz
Spectrum
0 ~ 2B ~ 4B ~ ~ 6B ~ 8B

in cm-1

16.8576314 = I (amu 2 )

Spherical Coordinate
x = r sin cos y = r sin sin tan = z = r cos cos = r= x2 + y2 + z2 z r y x

dV = r 2 sin drd d V =

r dr sin d
2 0

dVshell = 4 r 2dr I space =

0 0

F ( r , , )r 2 sin drd d

Solid angle : d = sin d d

2 2 2 2

sphere

d = 4

1 2 1 1 2 )+ 2 (sin )+ 2 = 2 + 2 + 2 = 2 (r (PS3) r r r sin r sin 2 2 x y z r

Harmonic Oscillator: Solving Eigenfunctions 2 2 h 1 2 1 d + kx = h + , = 0, 1, 2,... H = E 2 2 dx 2 2

You can solve this equation in two ways: (i) solve differential equations (tedious!) (ii) use properties of ladder operators (our choice)
lowering op a 2h a 0 = 0 2h d 0
1/ 2 1/ 2

ip x + = 1 a

h d 0 h d 0 x x + = + =0 0 0 dx dx
2

x 0 0 = N e x
1/ 2

/2

x e

/2

, = / h

raising op a + 2h

ip x + = + 1 + 1 a e x
2

+ ) (a 1/ 2 0 ( ! )

(2 !)

/2

1/ 2

H ( x )

Rotational Eigenfunctions

rotY ( , ) = ErotY ( , ) H

rot

x = cos dx = sin d 0 sin = 1 x 2 ( ) = P ( x )

associated Legendre polynomials

Solution: ( ) =
= J( J + 1)
| m |= 0, 1,...J