5.

61 Fall 2007 Lectures #12-15 page 1

THE HARMONIC OSCILLATOR

• Nearly any system near equilibrium can be approximated as a H.O.

• One of a handful of problems that can be solved exactly in quantum

mechanics

examples

m1 m2 B (magnetic
field)
A diatomic molecule µ
(spin
magnetic
moment)
E (electric
field)

Classical H.O.

m
k

X0 X

Hooke’s Law: (
f = −k X − X 0 ≡ −kx)
(restoring force)
d2x d2x ⎛ k ⎞
f = ma = m 2 = −kx ⇒ + x=0
dt dt 2 ⎜⎝ m⎠⎟
5.61 Fall 2007 Lectures #12-15 page 2

Solve diff. eq.: General solutions are sin and cos functions

k
() ( )
x t = Asin ω t + B cos ω t ( ) ω=
m
or can also write as

() (
x t = C sin ω t + φ )
where A and B or C and φ are determined by the initial conditions.

e.g. ()
x 0 = x0 ()
v 0 =0
spring is stretched to position x 0 and released at time t = 0.

Then

() ()
x 0 = A sin 0 + B cos 0 = x0 () ⇒ B = x0
dx
()
v 0 =
dt
()
= ω cos 0 − ω sin 0 = 0() ⇒ A=0
x=0

So ()
x t = x0 cos ω t ( )
k
Mass and spring oscillate with frequency: ω =
m
and maximum displacement x0 from equilibrium when cos(ωt)= ±1

Energy of H.O.
Kinetic energy ≡ K

2
1 1 ⎛ dx ⎞ 1 1
( ) ( )
2
K = mv 2 = m ⎜ ⎟ = m ⎡⎣ −ω x0 sin ω t ⎤⎦ = kx02 sin 2 ω t
2 2 ⎝ dt ⎠ 2 2

Potential energy ≡ U

dU 1 1 2
()
f x =−
dx
⇒ U = − ∫ f x dx =() ∫ ( kx )dx =
2
kx 2
=
2
( )
kx0 cos 2 ω t
5.61 Fall 2007 Lectures #12-15 page 3

Total energy = K + U = E

1 2 1 2
E=
2
( ) ( )
kx0 ⎡⎣sin 2 ω t + cos 2 ω t ⎤⎦ E= kx
2 0

x (t )
x 0(t )

0 t

-x0(t)

U K
1 2
kx E
2 0

0 t

Most real systems near equilibrium can be approximated as H.O.

e.g. Diatomic molecular bond A B

X
U

X
X0 A + B separated atoms

equilibrium bond length

5.61 Fall 2007 Lectures #12-15 page 4

dU 1 d 2U 1 d 3U
( ) ( ) (X − X ) (X − X ) (X − X )
2 3
U X = U X0 + 0
+ 0
+ 0
+!
dX X = X0
2 dX 2 X = X0
3! dX 3 X = X0

Redefine x = X − X 0 and ( )
U X = X0 = U x = 0 = 0 ( )
dU 1 d 2U 1 d 3U
()
U x =
dx
x+
2 dx 2
x +2

3! dx 3
x3 + !
x=0 x=0 x=0

real potential

H.O. approximation

dU
At eq. =0
dx x=0

For small deviations from eq. x 3 << x 2

1 d 2U 1 2
∴ U x ≈ () 2 dx 2
x2 ≡
2
kx
x=0
5.61 Fall 2007 Lectures #12-15 page 5

Total energy of molecule in 1D

m1 m2

X1 XCOM X2 X
M = m1 + m2 total mass
xrel
m1 m2
µ= reduced mass
m1 + m2
m1 X 1 + m2 X 2
X COM = COM position
m1 + m2
xrel = X 2 − X 1 ≡ x relative position

2 2 2 2
1 ⎛ dX ⎞ 1 ⎛ dX ⎞ 1 ⎛ dX ⎞ 1 ⎛ dx ⎞
K = m1 ⎜ 1 ⎟ + m2 ⎜ 2 ⎟ = M ⎜ COM ⎟ + µ ⎜ ⎟
2 ⎝ dt ⎠ 2 ⎝ dt ⎠ 2 ⎝ dt ⎠ 2 ⎝ dt ⎠

1 2
U= kx
2

2 2
1 ⎛ dX ⎞ 1 ⎛ dx ⎞ 1
E = K + U = M ⎜ COM ⎟ + µ ⎜ ⎟ + kx 2
2 ⎝ dt ⎠ 2 ⎝ dt ⎠ 2

COM coordinate describes translational motion of the molecule

2
1 ⎛ dX ⎞
Etrans = M ⎜ COM ⎟
2 ⎝ dt ⎠

QM description would be free particle or PIB with mass M

We’ll concentrate on relative motion (describes vibration)

2
1 ⎛ dx ⎞ 1
Evib = µ ⎜ ⎟ + 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

⎡ !2 d 2 1 2 ⎤
()
Ĥψ x = ⎢ − 2
+ kx ⎥ ψ x = Eψ x () ()
⎣ 2m dx 2 ⎦

K U

Note: replace m with µ (reduced mass) if m1 m2

Goal: Find eigenvalues En and eigenfunctions ψn(x )

Rewrite as:

( ) + 2m ⎡
E −
1
kx
d 2ψ x ⎤

dx 2
⎢
! 2 ⎣
2

2
()
⎥ ψ
x = 0
⎦

This is not a constant, as it was for P-I-B,

so sin and cos functions won’t work.

()
2
TRY: f x = e−α x 2
(gaussian function)

d2 f x( ) = −α e −α x 2 2
() ()
2

2
+ α 2 x 2 e−α x 2
= −α f x + α 2 x 2 f x
dx

d2 f x ( ) +α f
or rewriting,
dx 2 ( x) − α 2
()
x 2 f x = 0w

which matches our original diff. eq. if

2mE mk
α= and α2 =
!2 !2

! k
∴ E=
2 m
5.61 Fall 2007 Lectures #12-15 page 7

We have found one eigenvalue and eigenfunction

k 1 k
Recall ω= or ν=
m 2π m

1 1
∴ E= !ω = hν
2 2

This turns out to be the lowest energy: the “ground” state

For the wavefunction, we need to normalize:

() ()
2
ψ x = Nf x = Ne−α x 2
where N is the normalization constant

14
2
⎛α⎞
()
∞ ∞
∫ ∫
−α x2
ψ x dx = 1 ⇒ N 2
e =1 ⇒ N =⎜ ⎟
−∞ −∞ ⎝π⎠

π α

14
⎛α⎞
()
2
ψ0 x =⎜ ⎟ e−α x 2

∴ ⎝π⎠ ψ0 x ()
1 1 1
E0 = !ω = hν E0 = !ω
2 2 2
x

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

14
⎛α⎞ 1
()
2
ψ0 x =⎜ ⎟ e−α x 2
E0 = hν
⎝π⎠ 2
14
1 ⎛α⎞
()
ψ1 x = ⎜ ⎟
2⎝π⎠
( 2α x ) e
12 −α x 2 2
E1 =
3
2
hν
14
1 ⎛α⎞
ψ2 ()
x = ⎜ ⎟
8⎝π⎠
( 4α x 2
)
− 2 e−α x
2
2
E2 =
5
2
hν
14
1 ⎛α⎞
ψ3 ()
x = ⎜ ⎟
48 ⎝ π ⎠
(8α 32
x 3 − 12α 1 2 x e−α x ) 2
2
E3 =
7
2
hν

! !
12
⎛ km ⎞
with α =⎜ 2 ⎟
⎝! ⎠

These have the general form

14
⎛α⎞
()
ψn x =
1
1/ 2 ⎜
⎝ π ⎟⎠
(
H n α 1 2 x e−α x ) 2
2
n = 0,1,2,...
( 2 n!)
n

Normalization Gaussian
Hermite polynomial (pronounced “air-MEET”)

( )
H0 y = 1 even ( n = 0)
H ( y) = 2 y
1
odd ( n = 1)
H ( y) = 4 y − 2
2
2
even ( n = 2 )
H ( y ) = 8y − 12 y
3
3
odd ( n = 3)
H ( y ) = 16 y − 48y
4
4 2
+ 12 even ( n = 4 )
! !
5.61 Fall 2007 Lectures #12-15 page 9

() ()
2
ψ n x ψn x

7!ω

ψ3 x() E3 =
2

5!ω
ψ2 x() E2 =

3!ω
ψ1 x() E1 =

2
!ω

ψ0 x() E0 =
2

⎛ 1⎞
Energies are En = ⎜ n + hν
⎝ 2
⎟⎠

Note E increases linearly with n.

⇒ Energy levels are evenly spaced

⎛ 1⎞ ⎛ 1⎞
⎝
( )
En+1 − En = ⎜ n + 1 + ⎟ hν − ⎜ n + ⎟ hν = hν
2⎠ ⎝ 2⎠
regardless of n

There is a “zero-point” energy E0 = hν

2

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

5.61 Fall 2007 Lectures #12-15 page 10

Symmetry properties of ψ’s

ψ 0,2,4,6,.... are even functions ( ) ()

ψ −x = ψ x
ψ 1,3,5,7,.... are odd functions ψ ( −x ) = −ψ ( x )

Useful properties: (even) ⋅(even) = even

(odd) ⋅(odd) = even

(odd) ⋅(even) = odd

( )=
d odd (
d even )=
dx
(even ) dx
( odd )
∫ ( odd ) dx = 0 ∫ (even ) dx = 2 ∫ (even ) dx
∞ ∞ ∞

−∞ −∞ 0

Just from symmetry:

∗⎛ d⎞
() () ()
∞ ∞
x n
= ∫ −∞
ψ n∗ x xψ n x dx = 0 p n
= ∫−∞ n ⎜⎝ dx ⎟⎠ ψ n x dx = 0
ψ −ih

odd odd

Average displacement & average momentum = 0

IR spectroscopy ⇒ H.O. selection rules

Intensity of vibrational absorption features δ+ δ-

n’ = 1

Vibrational transition hν

n=0
5.61 Fall 2007 Lectures #12-15 page 11

2
dµ ∞ ∗
dx ∫−∞ n n '
Intensity I nn′ ∝ ψ xψ dx

1) Dipole moment of molecule must change as molecule vibrates ⇒

HCl can absorb IR radiation, but N2, O2, H2 cannot.

2) Only transitions with n′ = n ± 1 allowed (selection rule).

(Prove for homework.)

QUANTUM MECHANICAL HARMONIC OSCILLATOR &

TUNNELING

Classical turning points E

1 2
Classical H.O.: Total energy ET = kx
2 0
oscillates between K and U.
ET

Maximum displacement x0 occurs when

all the energy is potential.
x
-x0 x0
2ET
x0 = is the “classical turning point”
k

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.

1 2
kx
() ()
22
2 2 12kx
ψ3 x ψ 12 x
()212 xψ

()
2
ψ2 x

()
2
ψ1 x At high n, probability
density begins to look
classical, peaking at turning

() points.
2
ψ0 x

Non-zero probability at x > x 0!

() Prob. of (x > x 0, x < -x 0):

2
ψ3 x 1
⎛α⎞
()
∞ 2 ∞
2∫ ∫
2
ψ 02 x dx = 2 ⎜ ⎟ e−α x dx
⎝π⎠
−1 2 −1 2
α α

()
2
ψ2 x 2
()
∞
∫
2
= e− y dy = erfc 1
π1 2 1

“Complementary error function”

()
2
ψ1 x tabulated or calculated

numerically

()
2
Prob. of (x > x 0, x < -x 0) = erfc(1)

ψ0 x
= 0.16

Significant probability!

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.

Finite
()
ψ x ~ sin kx( ) ()
ψ x ~ e− γ x
barrier
V0
() (
ψ x ~ sin kx + φ )

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.

⎡
! 2 d 2 ⎤

Inside barrier: ⎢ −
2m dx 2
+ V0⎥ ()
ψ x = Eψ x ()
⎣
⎦

d 2ψ x ( ) = ⎡⎢ 2m (V −E ⎤)
or
dx 2 !
0
2 ()
⎥ ψ x ≡ γ 2ψ x ()
⎢⎣ ⎥⎦
1

(
⎡ 2m V0 − E ) ⎤⎥ 2

Solutions are of the form ()

ψ x = Be− γ x with γ =⎢
!2
⎢⎣ ⎥⎦

( )
12
Note γ ∝ V0 − E and γ ∝ 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.

System may be in a state other than an eigenstate, e.g.

2 2 1
ψ = c0ψ 0 + c1ψ 1 with c0 + c1 = 1 (normalization), e.g. c0 = c1 =
2
Full time-dependent eigenstates can be written as

( )
Ψ 0 x,t = ψ 0 x e () − iω 0 t
( ) ()
Ψ1 x,t = ψ 1 x e
− iω1t

where
1 1 3 3
!ω 0 = E0 = !ω vib ⇒ ω 0 = ω vib !ω 1 = E1 = !ω vib ⇒ ω 1 = ω vib
2 2 2 2

System is then time-dependent:

1 1
( )
Ψ x,t = e
− iω 0 t
()
ψ0 x + e
− iω1t
() () ( )
ψ 1 x = c0 t ψ 0 x + c1 t ψ 1 x () ( )
2 2
1 1
where ()
c0 t = e
− iω 0 t
c1 t = () e
− iω1t

2 2

What is probability density?

1⎡ ∗
( ) ( )
Ψ ∗ x,t Ψ x,t =
2⎣
ψ 0
x e ()
iω 0 t
+ ψ ∗
1
x e
iω1t
⎦⎣ ()
⎤ ⎡ψ 0 x e− iω 0 t + ψ 1 x e− iω1t ⎤
⎦ () ()
1 1
= ⎡ψ 0∗ψ 0 + ψ 1∗ψ 1 + ψ 1∗ψ 0 e ( 1 0 ) + ψ 0∗ψ 1e ( 1 0 ) ⎤ = ⎡⎣ψ 02 + ψ 12 + 2ψ 0ψ 1 cos ω vib t ⎤⎦
2⎣
i ω −ω t − i ω −ω t
⎦ 2 ( )

Probability density oscillates at the vibrational frequency!

5.61 Fall 2007 Lectures #12-15 page 15

ω t = 0, π 4, π 2, 3π 4, π
( )
2
Ψ x,t
() costψψω
01

()
2
ψ x
()211 xψ

()
2
ψ x
()200 xψ

x
2ψ 0ψ 1 cos (ω t )
()012costψψω ω t = 0, π 4, π 2, 3π 4, π

What happens to the expectation value <x>?

5.61 Fall 2007 Lectures #12-15 page 16

( ) ( )
∞
x = ∫ −∞
Ψ ∗ x,t x̂Ψ x,t dx
1 ∞⎡ ∗
=
2 ∫ −∞ ⎣ () () ()
ψ 0 x eiω 0 t + ψ 1∗ x eiω1t ⎤⎦ x ⎡⎣ψ 0 x e− iω 0 t + ψ 1 x e− iω1t ⎤⎦ dx ()
1 ∞
= ⎡ ∫ ψ 0∗ xψ 0 dx + ∫ ψ 1∗ xψ 1 dx + ∫ ψ 1∗ xψ 0 e ( 1 0 ) dx + ∫ ψ 0∗ xψ 1e ( 1 0 ) dx ⎤
∞ ∞ i ω −ω t ∞ − i ω −ω t

2 ⎣⎢ −∞ −∞ −∞ −∞ ⎦⎥
( )∫
∞
<x >0 = 0 <x >1 = 0 = cos ω vib t ψ 0 xψ 1 dx
−∞

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

∞
Vibrational amplitude is ∫ −∞
ψ 0 xψ 1 dx
1 1
⎛α⎞ 1 ⎛α⎞
() () ( 2α x ) e
4 2
4
−α x 2 2
ψ 0 x = ⎜ ⎟ e−α x 2
ψ1 x = ⎜ ⎟
12

⎝π⎠ 2⎝π⎠
1
⎛α⎞
() ( ) ()
2
4 −1 2
⇒ xψ 0 x = ⎜ ⎟ xe−α x 2 = 2α ψ1 x
⎝π⎠

( ) ∫ ( ) () ( ) ( )
∞ −1 2 ∞ −1 2 −1 2
∴ ∫ −∞
ψ 0 xψ 1 dx = 2α
−∞
ψ 02 dx = 2α x t = 2α cos ω vib t

Relations among Hermite polynomials

Recall H.O. wavefunctions

1
⎛α⎞4
()
ψn x =
1
1/ 2 ⎜
⎝ π ⎟⎠
H α 12
x (
e −α x 2
) 2
n = 0,1,2,...
( 2 n!)
n
n

Normalization Gaussian
Hermite polynomial
5.61 Fall 2007 Lectures #12-15 page 17

( )
H0 y = 1 even ( n = 0)
H ( y) = 2 y
1
odd ( n = 1)
H ( y) = 4 y − 2
2
2
even ( n = 2 )
H ( y ) = 8y − 12 y
3
3
odd ( n = 3)
H ( y ) = 16 y − 48y
4
4 2
+ 12 even ( n = 4 )
! !

Generating formula for all the Hn:

d n − y2
( ) ( )
n y2
Hn y = −1 e e
dy n

A useful derivative formula is:

( )=
dH n y d n − y2 n y2 d
n+1

( ) ( ) ( ) ( )
n y2 − y2
−1 2 ye e + −1 e e = 2 yH n y − H n+1 y
dy dy n dy n+1

Another useful relation among the Hn’s is the recursion formula:

( ) ( )
H n+1 y − 2 yH n y + 2nH n−1 y = 0 ( )
Substituting ( ) ( )
2 yH n y = H n+1 y + 2nH n−1 y above gives ( )
dH n y ( ) = 2nH
dy n−1 ( y)
Use these relations to solve for momentum <p>(t)

( ) ( )
∞
p = ∫ −∞

Ψ ∗ x,t p̂Ψ x,t dx

1 ∞⎡ ∗
= ∫
2 −∞ ⎣ () () ()
ψ 0 x eiω 0 t + ψ 1∗ x eiω1t ⎤⎦ pˆ ⎡⎣ψ 0 x e− iω 0 t + ψ 1 x e− iω1t ⎤

⎦ dx ()
1 ∞
= ⎡ ∫ ψ 0∗ pˆψ 0 dx + ∫ ψ 1∗ pˆψ 1 dx + ∫ ψ 1∗ pˆψ 0 e ( 1 0 ) dx + ∫ ψ 0∗ pˆψ 1e ( 1 0 ) dx ⎤
∞ ∞ i ω −ω t ∞ − i ω −ω t

2 ⎢⎣ −∞ −∞ −∞ −∞ ⎥⎦
<p >0 = 0 <p >1 = 0
5.61 Fall 2007 Lectures #12-15 page 18

1 1
d ⎛α⎞ ⎛α⎞
() ( −α x ) e ()
4 2
−α x 2 2
ψ0 x = ⎜ ⎟ = −⎜ ⎟ ψ1 x
dx ⎝π⎠ ⎝ 2⎠
1 1
⎛ α ⎞ i ω −ω t ⎛ α ⎞ iω t
ψ 1∗ p̂ψ 0 e ( )
dx = i! ⎜ ⎟ e ( 1 0 ) ∫ ψ 1∗ψ 1 dx = i! ⎜ ⎟ e vib
∞ 2 ∞ 2

∫
i ω1 − ω 0 t
∴
−∞ ⎝ 2⎠ −∞ ⎝ 2⎠

ψ 0∗ p̂ψ 1e ( 1 0 ) dx use relations among Hn’s

∞
∫
− i ω −ω t
To solve integral
−∞

d
dx
ψ1 x =
d ⎡
dx ⎣
()
2

(
⎦ ) d
N 1 H1 α 1 2 x e − α x 2 ⎤ = α 1 2 N 1 ⎡ H1 y e − y 2 ⎤
dy ⎣
2

⎦ ( )
d d
with y ≡ α1 2 x dy = α 1 2 dx dx = α −1 2 dy = α1 2
dx dy
d ⎡d ⎤
() ( ) ( )
2 2
ψ 1 x = α 1 2 N1 ⎢ H1 y e− y 2 − yH1 y e− y 2 ⎥
dx ⎣ dy ⎦
d
( )
H y = 2nH 0 y = 2H 0 y
dy 1
( ) ( )
1 1
( ) ( )
yH1 y = ⎡⎣ 2nH 0 y + H 2 y ⎤⎦ = H 0 y + H 2 y
2 2
( ) ( ) ( )
d ⎡ 1 ⎤ ⎡ 1 1 ⎤
() ( ) ( ) () ()
2 2
ψ 1 x = α 1 2 N1 ⎢ H 0 y e− y 2 − H 2 y e− y 2 ⎥ = α 1 2 N1 ⎢ ψ 0 x − ψ2 x ⎥
dx ⎣ 2 ⎦ ⎣ N0 2N 2 ⎦

d
ψ 0∗ p̂ψ 1e ( 1 0 ) dx = e ( 1 0 ) −i! ( )∫
∞ ∞
∫
− i ω −ω t − i ω −ω t
ψ 0∗ ψ dx
−∞ −∞ dx 1
⎡ 1 1 ⎤
( )
= e ( 1 0 ) −i! α 1 2 N1 ⎢
∞ ∞
∫ ∫−∞ 0 2 ⎥
− i ω −ω t
ψ 0∗ψ 0 dx − ψ ∗
ψ dx
⎣ N0 2N 2
−∞
⎦
1
N1 ⎛ α ⎞ − iω t
= e ( 1 0 ) −i! α 1 2 ( )
2
− i ω −ω t
= −i! ⎜ ⎟ e vib
N0 ⎝ 2⎠

Finally
5.61 Fall 2007 Lectures #12-15 page 19

⎡ 1
⎤ 1

() 1
(
⎛ α ⎞ 2 iω t
p t = ⎢ i! ⎜ ⎟ e vib − e vib
2⎢ ⎝ 2⎠
− iω t
) ⎥ = −! ⎛ α ⎞ 2 sin ω t
⎥ ⎜⎝ 2 ⎟⎠ ( vib )
⎢⎣ ⎥⎦

Average momentum also oscillates at the vibrational frequency.