Oscillator

The Harmonic Oscillator
Turning Points, A, -A
m
Stretch spring, let go.
Mass, m, oscillates back and forth.
Hooke's Law
F k x
force
d 2 x(t )
k
m x ( t )
dt 2

amplitude
linear restoring force
spring constant
F ma
&
& kx
mx
k
x ( t ) A sin
m
no friction
1/ 2
mass
Harmonic oscillator - oscillates sinusoidally.

A is how far the spring is stretched initially.
At the turning points, A, -A, motion stops.
All energy is potential energy.
Copyright Michael D. Fayer, 2007
Potential is Parabolic
F
A
V
V ( x)
x
V ( x ) k x dx
1
k x2
2
k 4 2 m 2 m 2
x
oscillator
frequency, Hz
oscillator
frequency, rad/s
Energy of oscillator is
E 1 / 2kA2
A - classical turning point.
A can take on any value. Energy is continuous, continuous range of values.
Quantum Harmonic Oscillator

Simplest model of molecular vibrations
Bond dissociation energy
Molecular potential energy

as a function of atomic separation.
x
Bonds between atoms act as "springs".
Near bottom of molecular potential well,
Molecular potential approximately parabolic
Harmonic Oscillator.
Potential V ( x )
Turning point
Kinetic energy
zero; potential
energy max.
1
k x2
2
Classical particle can never

be past turning point.
Turning
point
Turning
point
Particle can be stationary at bottom of well,

know position, x = 0; know momentum, p = 0.
x p 0
This can't happen for Q.M. harmonic oscillator.
Uncertainty Principle indicates that minimum Q.M. H.O. energy
One Dimensional Quantum Harmonic Oscillator

in the Schrdinger Representation
H E
(H E) 0
h2 d 2
1
2
H
k
x
2m d x 2 2
kinetic energy
Schrdinger Representation
potential energy
d 2 ( x ) 2m
2
2 2
x ( x ) 0.
2
2
dx
h
2 m / h
2mE
2
h
Substitute H and
definition of k.
Mult. by -2m/ 2.
Define
d 2 ( x )
2 2
x ( x) 0
2
dx
Find
( x)
d 2 ( x )
2 2
x ( x) 0
2
dx
Good from - .
Must obey Born Conditions

1. finite everywhere
2. single valued
3. continuous
4. first derivative continuous
Use polynomial method
1. Determine
( x ) for x
2. Introduce power series to make the large x solution correct for all x.
d 2 ( x )
2 2
x ( x) 0
2
dx
For very large x
2 x 2
Therefore, can be dropped.
d 2
2
2
2
dx
Try
2
x
2
Then,
x2
x2
d 2
2
2
x e 2 e 2
2
dx
This is negligible compared to the first term

as x goes to infinity.
Two solutions
2
x
2
This is O.K. at
2
x
2
This blows up at
Not finite everywhere.

Therefore, large x solution is
( x) e
2
x
2
For all x
( x) e
2
x
2
f ( x)
Must find this.
( x) e
2
x
2
f ( x)
Need second derivative in Schrdinger equation
x2
d 2 ( x)
e 2 ( 2 x 2 f f 2 x f ' f '')
2
dx
With
df
f '
dx
and
d 2 ( x)
d x2
Substitute
d2 f
f ''
d x2
into the original equation
d 2 ( x )
2 2
x ( x) 0
2
dx
and divide by
2
x
2
gives
f 2 x f f 0
Equation only in f.
Solve for f and have ( x ) .
divide by
1

f 2 x f
1 f 0.
substitute
x
f ( x ) H ( )
Gives
d 2 H ( )
d H ( )
1 H ( ) 0.
d 2
d
Hermite's equation
Substitute series expansion for H( )

H ( ) av a0 a1 a2 2 a3 3 L
dH ( )
a 1 a1 2 a2 3 a3 2 L
d
d 2H
1 a 2 2a2 6a3 L
2
d
d 2 H ( )
d H ( )
1 H ( ) 0.
d 2
d
2a2 6a3 12a4 2 20a5 3 L
2a1 4a2 2 6a3 3 L
substitute in series
The sum of these infinite
number of terms in all powers
of equals 0.
3
2
1
a
L 0.
1 ao
1 a1
1 a2
3
In order for the sum of all the terms in this expression to vanish identically
for any ,
the coefficients of the individual powers of must vanish separately.
To see this consider an unrelated simpler equation.
a5 x 5 a4 x 4 a3 x 3 a2 x 2 a1 x a0 0
Fifth degree equation. For a given set of the ai, there will be 5 values of x
for which this is true. However, if you know this is true for any value of x,
then the ai all must be zero.

1 a0 0

3 a1 0

5 a2 0

7 a3 0
2a 2
6a 3
12a4
20a5
Coefficients of like powers of .
In general
1 2 a 0

( +1)( +2)a 2
a 2
1 ( 2)
Even and odd series.

Pick a0 (a1 = 0), get all even coefficients.
Pick a1 (a0
= 0), get all odd coefficients.
Recursion Formula
Have expression in terms of series that satisfy the diff. eq.

But not good wavefunction.
Blows up for large |x| if infinite number of terms. (See book for proof.)
( ) e
e
2
2
H ( )
2 / 2
2 /2
For infinite number of terms and large |x|.

( x )
blows up
Unacceptable as a wavefunction.
Quantization of Energy
If there are a finite number of terms in the series for H( ),
wavefunction does not blow up. Goes to zero at infinity.
2 /2
The exponential goes to zero faster than n blows up.
To make series finite, truncate by choice of .
= (2n + 1) n is an integer.
Then, because
a 2
1 ( 2)
if a0 or a1 is set equal to zero (odd or even series)

series terminates after
=n
a finite number of terms.
Any value of with
= (2n + 1)
is O.K. Any other value of is no good.
Therefore,
2mE
(2n 1) 2 m / h
2
h
definition of
Solving for E
n0
definition of
1
En n h
2
E0 1/2 h
n is the quantum number
Lowest energy, not zero.
Energy levels equally spaced by h .

Hermite Polynomials
Energy Levels
1
En n h
2
H0 1
H1 2
Wavefunctions
n ( x ) N ne
1

Nn n
2 n !

1
2
2
2
Hn
2 m / h
H2 4 2 2
H 3 8 3 12
H 4 16 4 48 2 12
H 5 32 5 160 3 120
1
2
normalization constant
H 6 64 6 480 4 720 2 120
Lowest state
n = 0
1
4
0 ( x)
x2
2
1
4
0(x)
()2
-4 -3
-2
-1
Classical turning points
x2
2
2
h
k
x h / k
-4 -3
-2
-1
1/2 kx 2 1/2 h
potential
energy
total
energy
classical turning points - wavefunction extends into

classically forbidden region.
More wavefunctions - larger n, more nodes

n=1
n=2
n=3
-6 -4 -2 0 2 4
n=4
-6 -4 -2 0 2 4
n=5
-6 -4 -2 0 2 4 6
n=6
-6 -4 -2 0 2 4
-6 -4 -2 0 2 4
-6 -4 -2 0 2 4 6
Probability for n = 10
Classical turning points

~ = 4.6
Time oscillator spends

as a function of position.
-6
-4
-2
Looks increasingly classical.

For large object, nodes so closely spaced because n very large that
can't detect nodes.
Dirac Approach to Q.M. Harmonic Oscillator

Very important in theories of
2
p
1 2
H
kx
vibrations, solids, radiation
2m 2
Want to solve
eigenkets, normalized
H E E E
We know commutator relation
x , P i h1
To save a lot of writing, pick units such that
m 1
k 1
h 1
In terms of these units
1 2
2
H (P x )
2
x, P i 1
identity operator
Define operators
a
a a
i
(P i x)
2
1
i 2
(P i x)
a is the complex conjugate (adjoint) of a since P and x are Hermitian.
Then
1
a a [( P i x )( P i x )]
2
1 2
2
[P i x P i P x x ]
2
1 2
2
[ P i( x P P x) x ]
2
1 2
i
2
[ P x ] [ x, P ]
2
2
aa H 1
2
Hamiltonian
commutator
1
aa H 1
2
Similarly
1 2
2
a a [P i( x P P x) x ]
2
1
a aH 1
2
Therefore
1
H (a a a a )
2
and
a , a 1
Very different looking from Schrdinger Hamiltonian.
Can also show

[a , H ] a
[a , H ] a
Consider E; eigenket of H.
a E Q
Q Ea Ea
Q Q 0
scalar product of vector with itself
Q Q 0
only if
Q 0
We have
Q Q E a a E 0.
Then
1
1
E a a E E H 1 E (E ) E E 0
2
2
Therefore,
1
E
2
normalized, equals 1
Now consider
aH E Ea E
eigenket of H
H a E
commutator
a, H a H H a a
a E
( E 1)
these are same

rearrange
aH Haa
Operate H on ket, get same ket back

times number.
a E
Then,
( H a a) E a H E E a E
H a E
is eigenket with
eigenvalue, E - 1.
a E
( E 1)
eigenvalue
Ha E a E E a E
transpose
Ha E E a E a E
factor
eigenket
a E E 1
Maybe number multiplying.
Direction defines state, not length.
H a E
a is a lowering operator.
It gives a new eigenvector of H with one unit lower energy.
a E
( E 1)
a E E 1
2
a E E 2
3
a E E 3
Each application gives new ket one with one unit

lower energy.
Could keep doing this indefinitely,

1
but
E
2
Therefore, at some point we have a value of
E, call it E0,
such that if we subtract 1 from it
1
E0 1
2
But E0 - 1 can't be < 1/2. Therefore a E0 0
For eigenvector E0
a a E0
1
( H 1) E0
2
1
( E0 ) E0 0
2
1
2
1
E0 h
2
E0
not zero
in conventional
units
Raising Operator
Ea E
(H a a ) E
a H E
a H E
using the commutator
rearranging, operating, and factoring as before

H a E
a E
( E 1)
These are the same.
Therefore, a E
a E E 1
a
is an eigenket of H with eigenvalue E + 1.

number, but direction defines state
takes state into new state, one unit higher in energy.

It is a raising operator.
E0
is the state of lowest energy with eigenvalue (energy) 1/2.

Apply raising operator repeatedly. Each application gives state
higher in energy by one unit.
1
H E0 E0
2
eigenvalue, one unit higher in energy
3
E0 1
2
H a E0
H a
5
E0 2
2
7
E0 3
2
H a
E0
E0
1 3 5 7
E , , , ,L
2 2 2 2
En n
2
With normal units En n h

2
Same result as with Schrdinger Eq.

E0
is the state of lowest energy with eigenvalue (energy) 1/2.

Apply raising operator repeatedly. Each application gives state
higher in energy by one unit.
1
H E0 E0
2
eigenvalue, one unit higher in energy
3
E0 1
2
H a E0
H a
5
E0 2
2
7
E0 3
2
H a
E0
E0
1 3 5 7
E , , , ,L
2 2 2 2
En n
2
With normal units En n h

2
Same result as with Schrdinger Eq.

Eigenkets
E n
labeled with energy
1
2
Can relabel kets with quantum number

E n
1
n
2
Take n to be normalized.
Raising and Lowering operators
a n n n 1
a n n n 1
n n 1
a n ( n 1) n 1
n n
numbers multiply ket when raise

or lower
a n n n1
Will derive these below.

Consider operator
a a operating on n
a a n a
n n 1
n n
Therefore
a a n n n
is an eigenket of operator a a with eigenvalue n.
a a
number operator. Eigenvalue quantum number
Important in Quantum Theory of Radiation and Solids

a
and a
called creation and annihilation operators.

Number operator gives number of photons in radiation field
or number of phonons (quantized vibrations of solids) in crystal.
a n n n 1
a n n n 1
To find n and n
n 1 a n n
n 1 a n n
Take complex conjugate
n a n 1 n n1
Now
n a a n ( n 1)
because a a H 1/2
( H 1/2) n ( n 1/2 1/2) n
Work out
n a a n n a n 1 n
n n n 1 n
n a a n n 1 n n 1
from here
n 1 n n 1
But
n n1
2
Then n n n n 1
2
and n1 n1 n1 n 1
Therefore,
2
n 1 n n 1
True if
n n 1
n n
Using the occupation number representation with normal units

H
h (a a a a )
2
2 ( k / m )1/ 2
Consider H n
1
H n h a a n a a n
2
1
h a ( n 1)1/ 2 n 1 a n1/ 2 n 1
2
1
h ( n 1)1/ 2 ( n 1)1/ 2 n n1/ 2 n1/ 2 n
2
1
h (2n 1) n
2
1
h n n n h n
2
2
1
Therefore, n are eigenkets of H with eigenvalues n h .

2
Units in the raising and lowering operators

a
i
1
1/ 2
P
i
k
x
1/ 2
1/ 2
(2 h ) m
1
1
1/ 2
P
i
k
x
1/ 2
1/ 2
i (2 h ) m
aa
2 h
2k
h
h
x
2
k
1/ 2
1/ 2
1/ 2
Add operators, P cancels.
1/ 2
aa
hm
P i
2
2k
Many constants. This is the reason

why derivation was done in units
such that m 1 k 1 h 1 .
Need constants and units to work
problems.
1/ 2
x in terms of raising and lowering operators.
aa
Subtract operators, get P in terms of

raising and lowering operators.
Can use the raising and lowering operator representation to calculate

any Q.M. properties of the H. O.
Example
x 4 for ground state, average value of x4
4
0 x 0
In Schrdinger Representation
0
x 0dx
4
h
2k
1/ 2
aa
h
0 x 0
2k
0 ( a a )4 0
constant - C
C 0 a 0 0 a a 0 0 a a a 0 L
4
0 ( a )4 0
Many terms. Must keep order correct. Operators dont commute.
Could write out all of the terms, but easier way.

Any term that doesnt have same number of as and a+ = 0
Example
0a a a a 0 04
orthogonal = 0
Any operator that starts with a is zero.

L a 0 0
Can't lower past lowest state.
0 aa a a 0 0
Terms with 0 a are also zero

because
a 0 Q 0
0 Q Q 0 a
Only terms left are
0 aa aa 0
0 aa a a 0
2
h
4

0 x 0
0
a
a
a
a
0
0
a
aa
a 0
2k
a n n n1
a n ( n 1) n 1
0 aa aa 0 0 aa a 1
0 aa 0
0 aa 2
0a1
2 0a1
0 0 1
2 00 2
3 h2 2
0 x 0
4 k2
4
0 a a a a 0 0 a aa 1
No integrals.
2
2
Must be able to count.

Vibrational Wave Packet

A short optical pulse will excite many
vibrational levels of the excited state
potential surface.
pulse bandwidth
excited
electronic
state
vibrational levels
Launches
vibrational
wave packet
short pulse optical excitation
ground electronic state
Model Excited State Vibrational Wave Packet with H. O. States

Time dependent H. O. ket
n( t ) n e iEnt / h
Superposition representing wave packet on excited surface
t n n e int
n
Calculate position expectation value - average position - center of packet.
t xt
h
x
2k
1/ 2
aa
t x t m* e i m t n e i nt m x n
m
m* n e i ( n m ) t
m ,n
m aa n
2k
m aa n
if
only non-zero
m n1
Then
t xt
But
h
2k
n n 1
t xt
h
2k
n*1 n e i (n n1 ) t n n*1 n e i ( n n1 ) t n 1
and n n1
E h
n*1 n e i t n n*1 n e i t n 1
This expression shows that x time dependent.

Time dependence is determined by superposition of vibrational states
produced by radiation field.
Simplify
Take n large so
n >1
Also,
i =
Otherwise
j = 0
Each state same amplitude in superposition

for some limited set of states.
Using these
t xt
h 2
n e i t e i t
2k
n
t x t 2 2
h
n cos ( t )
2k n
Position oscillates as cos( t).
Wave packet on harmonic

potential surface.
Packet moves back and forth.
I2 example
Ground state excited to B state
~ 565 nm
20 fs pulse
band width ~700 cm-1
Level spacing at this energy
~69 cm-1
Take pulse spectrum to be rectangle and all excited same within bandwidth.
States n = 15 to n = 24 excited
(Could be rectangle)
Cos
+1 to -1
distance traveled twice coefficient of Cos
4 2
h
n
2k n
10 equal amplitude states.
2 0.1
k 2
1.05 1022 g
1.3 1013 Hz
Distance traveled = 1.06 .

Comparable to bond length.

Oscillator

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Oscillator

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The Harmonic Oscillator

linear restoring force

Harmonic oscillator - oscillates sinusoidally.

Copyright Michael D. Fayer, 2007

A - classical turning point.

A can take on any value. Energy is continuous, continuous range of values.

Copyright Michael D. Fayer, 2007

Quantum Harmonic Oscillator

Bond dissociation energy

Molecular potential energy

Classical particle can never

Particle can be stationary at bottom of well,

Copyright Michael D. Fayer, 2007

One Dimensional Quantum Harmonic Oscillator

Copyright Michael D. Fayer, 2007

Must obey Born Conditions

Copyright Michael D. Fayer, 2007

For very large x

This is negligible compared to the first term

Not finite everywhere.

Need second derivative in Schrdinger equation

into the original equation

Substitute series expansion for H( )

Copyright Michael D. Fayer, 2007

2a2 6a3 12a4 2 20a5 3 L

2a1 4a2 2 6a3 3 L

Copyright Michael D. Fayer, 2007

Coefficients of like powers of .

Even and odd series.

= 0), get all odd coefficients.

Have expression in terms of series that satisfy the diff. eq.

For infinite number of terms and large |x|.

Copyright Michael D. Fayer, 2007

The exponential goes to zero faster than n blows up.

To make series finite, truncate by choice of .

if a0 or a1 is set equal to zero (odd or even series)

a finite number of terms.

Copyright Michael D. Fayer, 2007

Any value of with

n is the quantum number

Lowest energy, not zero.

Energy levels equally spaced by h .

H 6 64 6 480 4 720 2 120

Copyright Michael D. Fayer, 2007

Classical turning points

classical turning points - wavefunction extends into

More wavefunctions - larger n, more nodes

Copyright Michael D. Fayer, 2007

Classical turning points

Time oscillator spends

Looks increasingly classical.

Copyright Michael D. Fayer, 2007

Dirac Approach to Q.M. Harmonic Oscillator

We know commutator relation

In terms of these units

Copyright Michael D. Fayer, 2007

a is the complex conjugate (adjoint) of a since P and x are Hermitian.

Copyright Michael D. Fayer, 2007

Very different looking from Schrdinger Hamiltonian.

Can also show

Copyright Michael D. Fayer, 2007

scalar product of vector with itself

these are same

Operate H on ket, get same ket back