Lecture 12: Harmonic Oscillator-II. The material in this lecture covers the following in Atkins. Section 12.

4 The energy levels Section 12.5 The wavefunction Lecture on-line Quantum mechanical harmonic oscillator (properties) (PowerPoint) Quantum mechanical harmonic oscillator (properties) (PDF format) Handout for this lecture Writeup on Harmonic Oscillator

Harmonic oscillator... Quantum mechanically .Hamiltonian

Review

We have for the harmonic oscillator Force constant 1 2 Epot = kx Displacement 2 where x is the displacement from equilibrium. Thus the hamiltonian is given by : H = E kin + Epot h2 d2 1 2 H= + kx 2 2 2m dx

Mass

1 2 V( x ) = kx 2

Harmonic oscillator... Quantum mechanically .Energy levels

Review
E

The energy evels of a harmonic oscillator are evenly paced with eparation , with = k/m)1/2. Even in its owest state, an oscillator has an nergy greater han zero.

v=6

1 E = h( + v ) 2
11 h 2 9 h 2 7 h 2 5 h 2 3 h 2 1 h 2 x

v=5
v=4

v=3

v=2

v=1
v=0

Harmonic oscillator...Quantum mechanically.... Wavefunction

We have the general solution y2 v ( x ) = N v exp H v (y) ; y = x/ 2
It is readilly shown that Nv = so v (x) = 1
1 2 2 v v!

1
1 2 2 v v!

y2 exp Hv ( y ) 2

Harmonic oscillator...Quantum mechanically.... Wavefunction

bell shaped Gaussian function

The graph of the Gaussian function, f(x) = e -x2.

Harmonic oscillator...Quantum mechanically.... Wavefunction

v Hv Hermit polynominals _________________________ 0 1 1 2y 2 3 4 5 4y 2 - 2 8y 3 - 12y 16y 4 - 48y 2 + 12 32y 5 - 160y 3 + 120y

6 64y 6 - 48y 4 + 72y 2 - 120 _____________________________

Note that H v for v odd (1, 3, 5, 7,..) is odd : H v (y) = - H v ( y) Note that H v for v even (0, 2, 4, 6, 8...) is even : H v (y) = H v ( y)

Harmonic oscillator...Quantum mechanically.... Wavefunction

Pr operties of Hermit polynominals :

Here
H" v 2yH'v + 2vHv = 0

H" = v

d2Hv dy 2

Hv +1 = 2yHv 2vHv 1 (recursionformula)

' = d Hv Hv

dy

Hv 'Hv e y dy =
2

1 2 2 v v!

vv '

Harmonic oscillator...Quantum mechanically.... Wavefunction

v (x) =

1
1 2 2 v v!

y2 exp Hv ( y ) 2

For the groundstate v = 0 of the harmonic oscillator we have the wavefunction y2 1 o (x) = exp H0 ( y ) 1 2 2 y2 1 exp = 1 2 2
The normalized wavefunction and probability distribution (shown also by shading) for the lowest energy state of a harmonic oscillator.

Harmonic oscillator...Quantum mechanically.... Wavefunction

v (x) =

1
1 2 2 v v!

y2 exp Hv ( y ) 2

For v = 1

1( x ) = 2

1
1 2 2

y2 exp y 2

The normalized wavefunction and probability distribution (shown also by shading) for the first excited state of a harmonic oscillator.

Harmonic oscillator...Quantum mechanically.... Wavefunction

v (x) =

1
1 2 2 v v!

y2 exp Hv ( y ) 2

The normalized wavefunctions for the first five states of a harmonic oscillator. Note that the number of nodes is equal to v and that alternate wavefunctions are symmetrical or antisymmetrical about y = 0 (zero displacement).

Harmonic oscillator...Quantum mechanically.... Wavefunction

Particle can be found outside clasical region

y2 v ( x ) = Nv exp Hv ( y ) 2

Harmonic oscillator...Quantum mechanically.... Wavefunction

v (x) =

1
1 2 2 v v!

y2 exp Hv ( y ) 2

The probability distributions for the first five states of a harmonic oscillator represented by the density of shading. Note how the regions of highest probability (the regions of densest shading) move towards the turning points of the classical motion as v increases.

Harmonic oscillator...Quantum mechanically .Energy levels

Potential energy increases more suddenly for particle in a box

1 2 V = kx 2
V=0

Particle confined in box

Particle confined in harmonic potential

Harmonic oscillator...Quantum mechanically .Energy levels Comparison of energy levels in harmonic oscillator and particle in a box E
Energy levels 25 h 2 8mL n=5 in particle in box E= n h
2 2 2
2

n=4

h2 16 8mL2 h2 8mL2 2 4 h 2 8mL h2 8 mL 2

11 h 2 v=5 9 h 2
5 2h v=2 3 h 2 v=1 1 2h v=0

Energy levels for harmonic oscillator

8mL n = 1, 2, 3 E = (2n + 1)

1 E = h( + v ) v=4 2 7 h 2 v=3 v = 0, 1, 2, 3 Spacing E = h

9 n=3

n=2

8mL2 n=1 Particle-in-box

Harmonic oscillator

Zero-point Energy

Harmonic oscillator...Quantum mechanically.... properties

Expectation values = * ( x ) v ( x )dx v

x = * ( x )x v ( x )dx v

y2 v ( x ) = N v exp H v ( y ); y = x/ 2

y2 y2 2 = N v exp[ ]H v (y)x exp[ ]H v (y)dx 2 2 -

y2 x y2 2 2 exp[ ]H ( y )( )exp[ ]H ( y )d( x ) = Nv v v 2 2 -

y2 y2 2 = N v 2 exp[ ]H v (y)y exp[ ]H v (y)dy 2 2 -
2 2 exp[ y 2 ]H ( y )yH ( y )dy = Nv v v -

Harmonic oscillator...Quantum mechanically.... properties Properties of Hermit 2 2 exp[ y 2 ]H ( y )yH ( y )dy = Nv polynominals : v v
-

H v +1 = 2 yH v 2 vH v 1 1 yH v = H v +1 + vH v 1 2
1 2 = N v 2 exp[ y 2 ]H v (y)H v +1 (y)dy 2 -
2 2 v exp[ y 2 ]H ( y )H +Nv v v 1 ( y )dy -

H" 2 yH' + 2 vH v = 0 v v H v +1 = 2 yH v 2 vH v 1 (recursionformula)

y 2 dy = H v 'H v e 1 2 2 v v! ' vv

= v,v+1 + v,v-1 = 0 + 0 <x> = 0

Harmonic oscillator...Quantum mechanically.... properties

You will show in assigned questions : x 2 = * ( x )x 2 v ( x )dx v h 1 ( + v) = k 2

-

We note that < x 2 > increases with v as the probability to find the particle at the turning points increases. Also < x 2 > decreases with k

Harmonic oscillator...Quantum mechanically.... properties

It follows 1 1 * V = k x 2 = k v ( x )x 2 v ( x )dx 2 2 - 1 1 1 1 1 1 = kh(v + ) = h(v + ) = E 2 2 k 2 2 2 We can find the average kinetic energy from 1 1 V + T =< E > E + T = E T = E 2 2

p2 = x thus < T > = 1 < p2 > E ; x We also have T 2 2m 2m 1 x x or < p2 > = 2mE; < p2 > = 2mh( + v ) 2 You are being asked to shown in assigned problems < px > = 0

Harmonic oscillator...Quantum mechanically.... properties

In general for a potential V = axb It can be shown that b T = V "Virial Theorem" 2 2 V = E b+2 b T = E b+2

Taylor expansion Harmonic oscillator...Quantum mechanically.. Vibration Spectroscopy 0 0 dV V(R) = V(R e ) + ( ) R e dR

small 2V 3V 1 d 2 + 1 ( d ) R 3 + ... + ( 2 ) R e e 2 dR 8 dR 3

1 d2V 1 d2V V(R) = ( 2 ) R e 2 = kR e 2 ;( 2 ) = k 2 dR 2 dR

Harmonic oscillator...Quantum mechanically

1 d2V 1 d2V V(R) = ( 2 ) R e 2 = kR e 2 ;( 2 ) = k 2 dR 2 dR

The force constant is a measure of the curvature of the potential energy close to the equilibrium extension of the bond. A strongly confining well (one with steep sides, a stiff bond) corresponds to high values of k.

Harmonic oscillator...Quantum mechanically

We note relation between bond energy D ; bond order and force constant k

Harmonic oscillator...Quantum mechanically

Alternative descriptions of the vibrations of CO2. (a) The stretching modes are not independent, and if one CO group is excited the other begins to vibrate. (b) The symmetric and antisymmetric stretches are independent, and one can be excited without affecting the other: they are normal modes. (c) The two perpendicular bending motions are also normal modes.

Harmonic oscillator...Quantum mechanically

The three normal modes of H2O. The mode v2 is predominant ly bending, and occurs at lower wavenumber than the other two.

Harmonic oscillator...Quantum mechanically

What you should learn from this lecture 1. You are not required to remember the hermit polynomials and their relations. However you should be able to make use of the two tables Pr operties of Hermit v Hv polynominals : _________________________ Hermit polynominals 0 1 H" 2yH'v + 2vHv = 0 v 1 2y

2 3 4 5

4y 2 - 2 8y 3 - 12y 16y 4 - 48y 2 + 12 32y 5 - 160y 3 + 120y

6 4 2

Hv +1 = 2yHv 2vHv 1 (recursionformula)

6 64y - 48y + 72y - 120 _____________________________

Hv 'Hv e y dy =
2

1 2 2 v v!

vv '

What you should learn from this lecture

2. You should remember Hv is odd for v odd and even for v even. You should understand the meaning of odd and even functions

3. You should understand the problem assigned to this lecture on the vibrating diatomic molecule A - B