5.

61 Fall 2007

Lectures #12-15

page 1

THE HARMONIC OSCILLATOR

One of a handful of problems that can be solved exactly in quantum mechanics examples m1 A diatomic molecule

m2
(spin magnetic moment)

B (magnetic field)

E (electric field)

Classical H.O.

X0
Hookes Law: (restoring force)

f = k X X 0 kx

d2x f = ma = m 2 = kx dt

d2x k + x=0 m dt 2

5.61 Fall 2007

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Solve diff. eq.:

General solutions are sin and cos functions

x t = A sin t + B cos t
or can also write as

()

( )
(

( )

k m

x t = C sin t +

()

where A and B or C and are determined by the initial conditions. e.g.

x 0 = x0

spring is stretched to position x 0 and released at time t = 0. Then

()

v 0 =0

()

x 0 = A sin 0 + B cos 0 = x0 v 0 =
So

()

()

()

B = x0 A=0

()
()

dx dt

= cos 0 sin 0 = 0
x=0

()

()

x t = x0 cos t

( )
k m

Mass and spring oscillate with frequency: = and maximum displacement Energy of H.O. Kinetic energy K

x0

from equilibrium when cos(t)= 1

2 1 1 dx 1 1 2 2 K = mv 2 = m = m x sin t = kx sin t 0 2 2 dt 2 2 0

( )

( )

Potential energy U

f x =

()

dU dx

U = f x dx =

()

1 kx dx = kx ( ) 2

1 2 kx0 cos 2 t 2

( )

5.61 Fall 2007

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Total energy = K + U = E

E=
x (t ) x 0(t )
0

1 2 kx0 sin 2 t + cos 2 t 2

( )

( )

E=

1 2 kx 2 0

-x0(t)

1 2 kx 2 0

K E

Most real systems near equilibrium can be approximated as H.O. e.g. Diatomic molecular bond A

B
X

U X A + B separated atoms

X0

equilibrium bond length

5.61 Fall 2007

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U X = U X0

( )

( )

dU + dX

X = X0

(X X )
0

1 d 2U + 2 dX 2

(X X )
0 X = X0

1 d 3U + 3! dX 3

(X X )
0 X = X0

+!

Redefine x = X X 0

and

U X = X0 = U x = 0 = 0
1 d 2U x+ 2 dx 2 x=0 1 d 3U x + 3! dx 3 x=0
2

dU U x = dx

()

x3 + !
x=0

real potential H.O. approximation

At eq.

dU dx

=0
x=0

For small deviations from eq. U x

x 3 << x 2
1 d 2U 2 dx 2 x2
x=0

()

1 2 kx 2

5.61 Fall 2007

Lectures #12-15

page 5

Total energy of molecule in 1D

m1

m2
XCOM xrel X2 X

M = m1 + m2

total mass reduced mass

X1

m1 m2 m1 + m2

X COM =

m1 X 1 + m2 X 2 m1 + m2

COM position relative position

xrel = X 2 X 1 x
2

1 dX 1 dX 1 dX 1 dx K = m1 1 + m2 2 = M COM + 2 dt 2 dt 2 dt 2 dt

U=

1 2 kx 2
2 2

1 dX 1 dx 1 E = K + U = M COM + + kx 2 2 dt 2 dt 2
COM coordinate describes translational motion of the molecule

Etrans

1 dX = M COM 2 dt

QM description would be free particle or PIB with mass M Well concentrate on relative motion (describes vibration)

Evib

1 dx 1 = + kx 2 2 dt 2

and solve this problem quantum mechanically.

5.61 Fall 2007

Lectures #12-15

page 6

THE QUANTUM MECHANICAL HARMONIC OSCILLATOR

()

()

()
m2

Note: replace m with (reduced mass) if m1

Goal: Find eigenvalues En and eigenfunctions n(x ) Rewrite as:

d 2 x dx 2

( ) + 2m
E
1
kx
! 2
2

x = 0

()

This is not a constant, as it was for P-I-B, so sin and cos functions wont work. TRY:

f x = e x
d2 f x dx
2

()

(gaussian function)

( ) = e

x 2 2

+ 2 x 2 e x d2 f x dx
2

= f x + 2 x 2 f x

()
2

()

or rewriting,

( ) + f

( x)

x2 f x = 0w

()

which matches our original diff. eq. if

2 mE !2

and

2 =

mk !2

E=

! k 2 m

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Lectures #12-15

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We have found one eigenvalue and eigenfunction

Recall

k m

or

1 2

k m

E=

1 1 ! = h 2 2

This turns out to be the lowest energy: the ground state For the wavefunction, we need to normalize:

x = Nf x = Ne x

()

()

where N is the normalization constant

x dx = 1

()

x2

=1

N =

14

()

x =

14

e x

E0 =

1 1 ! = h 2 2

0 x
x

()

E0 =

1 ! 2

Note 0 x is symmetric. It is an even function: 0 x = 0 x

()

()

( )

There are no nodes, & the most likely value for the oscillator displacement is 0. So far we have just one eigenvalue and eigenstate. What about the others?

5.61 Fall 2007

Lectures #12-15

page 8

() ()

x =

14

e x
14

E0 =
12 x 2 2

1 h 2 3 h 2 5 h 2 7 h 2

1 1 x = 2

( 2 x ) e ( 4 x (8
2

E1 =
2

2 3

() ()

1 x = 8

14

2 e x

E2 =

1 x = 48

14

32

x 3 12 1 2 x e x
12

E3 = !

!
with

km = 2 !

These have the general form

n x =

()

( 2 n!)
n

1/ 2

14

H n 1 2 x e x

n = 0,1,2,...

Normalization Gaussian Hermite polynomial (pronounced air-MEET)

( ) H ( y) = 2 y H ( y) = 4 y 2 H ( y ) = 8 y 12 y H ( y ) = 16 y 48 y
H0 y = 1
1 2 2 3 3 4 4

+ 12

( n = 0) odd ( n = 1) even ( n = 2 ) odd ( n = 3) even ( n = 4 )

5.61 Fall 2007

Lectures #12-15

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n x

()
() () () ()
7 !
2 5! 2 3! 2 !
2

n x

()

3 x

E3 =

2 x

E2 =

1 x

E1 =
E0 =

0 x

Energies are

En = n +

1 h 2

Note E increases linearly with n. Energy levels are evenly spaced

1 1 En +1 En = n + 1 + h n + h = h 2 2

regardless of n

There is a zero-point energy

E0 =

1
h 2

E = 0 is not allowed by the Heisenberg Uncertainty Principle.

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Lectures #12-15

page 10

Symmetry properties of s

0,2,4,6,....

are even functions are odd functions

x = x

1,3,5,7,....

( ) () ( x ) = ( x )

Useful properties:

(even) (even) = even

d odd dx

( )=

(even )

d even dx

)=

( odd )
0

( odd ) dx = 0

(even ) dx = 2 (even ) dx

Just from symmetry:

n x x n x dx = 0

()

()

d ih x dx = 0 n dx n

()

odd

odd

Average displacement & average momentum = 0

IR spectroscopy

H.O. selection rules +

Intensity of vibrational absorption features

n = 1
Vibrational transition

h n=0

5.61 Fall 2007

Lectures #12-15

page 11

Intensity

I nn

d x dx dx n n '

1)

Dipole moment of molecule must change as molecule vibrates HCl can absorb IR radiation, but N2, O2, H2 cannot. Only transitions with (Prove for homework.)

2)

n = n 1

allowed (selection rule).

QUANTUM MECHANICAL HARMONIC OSCILLATOR & TUNNELING

E
1 2 kx 2 0

oscillates between K and U. Maximum displacement x0 occurs when all the energy is potential.

ET

-x0

x0

x0 =

2 ET k

is the classical turning point

The classical oscillator with energy ET can never exceed this displacement, since if it did it would have more potential energy than the total energy.

5.61 Fall 2007

Lectures #12-15

page 12

Quantum Mechanical Harmonic Oscillator.

3 x

()

12 x ()212 x
2

()

1 2 kx 22 12kx

2 x
1 x

()

() ()

0 x

At high n, probability density begins to look classical, peaking at turning points.

3 x

()

Non-zero probability at x > x 0! Prob. of (x > x 0, x < -x 0):

2 x
1 x

()

2 =

1 2

2 0 x dx = 2

()

1 2

1 2

e x dx

() ()

Complementary error function

2 1 2

e y dy = erfc 1

()

0 x

5.61 Fall 2007

Lectures #12-15

page 13

The oscillator is tunneling into the classically forbidden region. This is a purely QM phenomenon! Tunneling is a general feature of QM systems, especially those with very low mass like e- and H.

x ~ sin kx

()

( )

x ~ e x
V0

()

Finite barrier

x ~ sin kx +

()

x Even though the energy is less than the barrier height, the wavefunction is nonzero within the barrier! So a particle on the left may escape or tunnel into the right hand side.
Inside barrier:

! 2 d 2
+ V x = E x 0 2 2 m dx

()

()
() ()
( )

1 2

or

d 2 x dx 2

2 m (V ( )=

E x 2 x 2 !
0

Solutions are of the form

x = Be x

()

with

2 m V0 E = !2

Note

V0 E

12

and

m1 2

If barrier is not too much higher then the energy and if the mass is light, then
tunneling is significant.
Important for protons (e.g. H-bond fluctuations, tautomerization)

5.61 Fall 2007

Lectures #12-15

page 14

Important for electrons (e.g. scanning tunneling microscopy)

Nonstationary states of the QM H.O.

= c0 0 + c1 1

with

c0 + c1 = 1 (normalization), e.g.

c0 = c1 =

1 2

Full time-dependent eigenstates can be written as

0 x, t = 0 x e
where

( )

()

i 0 t

1 x , t = 1 x e

( )

()

i1t

! 0 = E0 =

1 1 ! vib 0 = vib 2 2

! 1 = E1 =

3 3 ! vib 1 = vib 2 2

System is then time-dependent:

x, t = where

( )

1 2

i 0 t

0 x +
e
i 0 t

()

1 2

i1t

1 x = c0 t 0 x + c1 t 1 x
1 2 e
i1t

()

() ( )

() ( )

c0 t =

()

1 2

c1 t =

()

What is probability density?

1 i 0 t i1t 0 x e i 0 t + 1 x e i1t x e + x e 0 1 2 1 1 2 i t i t = 0 0 + 1 1 + 1 0e ( 1 0 ) + 0 1e ( 1 0 ) = 0 + 12 + 2 0 1 cos vibt 2 2 x, t x, t =

( ) ( )

()

()

()

()

Probability density oscillates at the vibrational frequency!

5.61 Fall 2007

Lectures #12-15

page 15

( ) () cost
x, t
01

t = 0, 4, 2, 3 4,

1 x ()21 x

()

0 x ()20 x

()

2 0 1 cos ( t ) () 012cost

t = 0, 4, 2, 3 4,

What happens to the expectation value <x>?

5.61 Fall 2007

Lectures #12-15

page 16

x = =

x , t dx x, t x

( ) ( )

1 i t 0 x ei 0 t + 1 x e 1 x 0 x e i 0 t + 1 x e i1t dx 2 1 i t i t = 0 x 0 dx + 1 x 1 dx + 1 x 0 e ( 1 0 ) dx + 0 x 1e ( 1 0 ) dx 2

()

()

()

()

<x >0 = 0

<x >1 = 0

= cos vib t

0 x 1 dx

<x>(t) oscillates at the vibrational frequency, like the classical H.O.! Vibrational amplitude is

0 x 1 dx
2

2 0 x = e x

()

1 4

1 x =
1 4

()

1 2

1 4

( 2 x ) e
12

x 2 2

2 x 0 x = xe x 2 = 2

()

( )

1 2

1 x

()
1 2

0 x 1 dx = 2

( )
1 2

2 0 dx = 2

( )

1 2

x t = 2

() ( )

cos vib t

Relations among Hermite polynomials

n x =

()

( 2 n!)
n

4 12 x 2 H x e n 1/ 2

n = 0,1,2,...

Normalization Gaussian Hermite polynomial

5.61 Fall 2007

Lectures #12-15

page 17

( ) H ( y) = 2 y H ( y) = 4 y 2 H ( y ) = 8 y 12 y H ( y ) = 16 y 48 y
H0 y = 1
1 2 2 3 3 4 4

+ 12

( n = 0) odd ( n = 1) even ( n = 2 ) odd ( n = 3) even ( n = 4 )

!
Generating formula for all the Hn:

Hn
A useful derivative formula is:

( ) ( )

d n y2 y = 1 e e dy n
n y2

dH n y dy

( )=

( )

n +1 n y2 d d n y2 y2 1 2 ye e + 1 e e = 2 yH n y H n +1 y dy n dy n +1 n y2

( )

( )

( )

Another useful relation among the Hns is the recursion formula:

H n +1 y 2 yH n y + 2 nH n 1 y = 0
Substituting

( )

( )

( )

2 yH n y = H n +1 y + 2 nH n 1 y above gives
dH n y dy

( )

( )

( )

( ) = 2nH

n 1

( y)

Use these relations to solve for momentum <p>(t)

p = =

x , t dx x, t p

( ) ( )

1 i t 0 x e i 0 t + 1 x e i1t
dx 0 x ei 0 t + 1 x e 1 p 2 1 i t i t 0 dx + 1 1 dx + 1 0 e ( 1 0 ) dx + 0 1e ( 1 0 ) dx = 0 p p p p 2

()

()

()

()

<p >0 = 0

<p >1 = 0

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Lectures #12-15

page 18

d 0 x = dx

()

1 4

( x ) e
1 2

x 2 2

= 1 x 2

1 2

()
1 2

0 e ( 1 p

i 1 0 t

i t dx = i! e ( 1 0 ) 1 1 dx = i! ei vibt 2 2

To solve integral

i t 1e ( 1 0 ) dx use relations among Hns 0 p

2 2 d d d 1 x = N 1 H1 1 2 x e x 2 = 1 2 N 1 H1 y e y 2 dx dx dy

()

( )

with

y 1 2 x

dy = 1 2 dx

dx = 1 2 dy

d d = 1 2 dx dy

2 2 d d 1 x = 1 2 N1 H1 y e y 2 yH1 y e y 2 dx dy d H y = 2 nH 0 y = 2 H 0 y dy 1 1 1 = H0 y + H2 y yH1 y = 2 nH y + H y 0 2 2 2

()

( )

( )

( )

( )

( )

( )

( )

( )

( )

( )

1 2 2 d 1 1 1 x = 1 2 N1 H 0 y e y 2 H 2 y e y 2 = 1 2 N1 0 x 2 x dx 2 2N2 N0

()

( )

( )

()

()

i t i t 1e ( 1 0 ) dx = e ( 1 0 ) i! 0 p

( )
1 2

d dx dx 1 dx 0 2

1 i t = e ( 1 0 ) i! 1 2 N 1 N0

( ) ( )

0 0 dx

1 2N2

i t = e ( 1 0 ) i! 1 2

i t = i! e vib N0 2 N1

Finally

5.61 Fall 2007

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page 19

1 2 i t 1 i t p t = i! e vib e vib 2 2

()

1 = ! 2 sin t vib 2

Average momentum also oscillates at the vibrational frequency.