Bound and Unbound States

h d x
E x
V x x
2
2m dx
2

To understand the nature of solutions, compare energy to potential at

Classically, there are two types of solutions to these equations
Bound States are when E < V().
Unbound states are when E > V()
Quantum mechanically, there
are bound and unbound states as
well, with the same criteria
Bound states are a little
easier to understand, so
V(x)
well do these first

E > V()
E < V()

Wave Function Constraints

The wave function (x) must be continuous
Its derivative must exist everywhere
Its derivative must be continuous*
Its second derivative must exist everywhere*
The wave function must be properly normalized
Must not blow up at
*Except where V(x) is infinite
There are exceptions and ways around this problem

1.
2.
3.
4.
5.

h2 d 2
E
V x
2
2m dx
1

Normalization
What if the wave function is not properly normalized?
If the integral is finite, multiply by a constant to fix it
Modified wave satisfies Schrdinger
If the integral is infinite, it gets complicated
For bound states, this is still trouble
For unbound states, it is okay

dx

dx A

Define x x
Then

1 x dx

The 1D infinite square well (1)

h2 d 2
E
V x
2
2m dx
0 if 0 x L
V x
otherwise

V(x)

Outside of the well, the wave function must vanish x

In remaining region, we need to solve differential equation
2
2
What functions are minus their
h d
E
second derivative?
2
2m dx
We prefer real
Boundary Conditions
Must vanish at x = 0
And at x = L
0 L sin kL
Where does sin vanish?
Dont worry about derivative because V(x) blows up there

0 if x 0 or x L

x cos kx
x sin kx
x e ikx
n
k
L

The 1D infinite square well (2)

x sin kx

h2 d 2
E
2m dx 2

n
k
L

h2 d 2
h2 k d
h2 k 2
E sin kx
sin kx
cos kx
sin kx
2
2m dx
2m dx
2m
h2 k 2
2 h2 n 2
E

En
2
2m
2mL

n 1, 2,3,K

n=1
n=2
n=3
n=4

nx
x sin

mL2E/ 2

Energy Diagram

1D Infinite Square Well (3)

BUT WAIT: What about normalization?

x dx 0
2

nx
x
L
2 nx

sin
sin
dx L

L
L
2 2 n

2
nx
sin
if 0 x L
L
L
0
otherwise

n x

The most general solution is

superposition of this solution

x, t cn n x exp iEnt h
n

To fix it: multiply by (2/L).

nx
x sin

2 h2 n 2
En
2mL2
n 1, 2,3,K

L
1
2

The Finite Square Well (1)

h d
E
V x
2
2m dx
0 if x 12 L
V x
V0 otherwise
2

We need to solve equation in all three regions; this takes work

In region II, we get solutions like before
No longer necessary that it vanish at the boundaries
In regions I and III, we solve a different equation:

h2 d 2
E
V0
2
2m dx

h2 d 2
V0 E
2
2m dx

If we are looking at bound state (E < V0),

in these regions, we get exponentials

x e x

II

III

x cos kx
x sin kx

h2 k 2
E
2m
h2 2
V0 E
2m

2mE
2m V0 E
2
k 2

h
h2
x
x
I x Ae Be
2

The Finite Square Well (2)

I

II x C cos kx D sin kx

II

III

III x Ee x Fe x

Wave function must not blow up at B E 0

Wave function must be continuous at x = L

I 12 L II 12 L
II L III L
1
2

1
2

Ae L 2 C cos kL 2 D sin kL 2
Fe

L 2

C cos kL 2 D sin kL 2

Derivative of wave function must be continuous at x = L

I 12 L II 12 L
12 L
II 12 L III

A e L 2 Ck sin kL 2 Dk cos kL 2
F e L 2 Ck sin kL 2 Dk cos kL 2

2mE
2m V0 E
2
k 2

h
h2
x
x
I x Ae Be
2

The Finite Square Well (2)

I

II x C cos kx D sin kx

II

III

III x Ee x Fe x

Wave function must not blow up at B E 0

Wave function must be continuous at x = L

I 12 L II 12 L
II L III L
1
2

1
2

Ae L 2 C cos kL 2 D sin kL 2
Fe

L 2

C cos kL 2 D sin kL 2

Derivative of wave function must be continuous at x = L

I 12 L II 12 L
12 L
II 12 L III

A e L 2 Ck sin kL 2 Dk cos kL 2
F e L 2 Ck sin kL 2 Dk cos kL 2

The Finite Square Well (3)

2

75h
V0
2
mL

n=4
n=3
n=2
n=1

Solve all these equations simultaneously

Normalize the final wave function
Wave function penetrates into forbidden region
Oscillates when E > V(x)
Damps when E < V(x)
Energies decreased slightly compared to infinite square well
Finite number of bound states
Due to finite extension and depth of potential well

Energy
Diagram

Infinite
Well

The Harmonic Oscillator (1)

h2 d 2
E
V x
2
2m dx

V x 12 kx 2 12 m 2 x 2

d 2
2mE
m 2 2 2
2 2 x
2
dx
h
h

At large x, the behavior is governed (mostly) by the x2 term d

2
Now we guess
dx
d
m x
Dont want it blowing up
:

dx
h
at infinity!
d
m
Our strategy:

xdx
Check that this works

h
Find more solutions and check them
2
2

m x
exp

2h

m x
:

h

m x
ln
2h

m x 2
exp

2h

The Harmonic Oscillator (2)

h d 1
2
2
E

m x
2
2
exp
2m dx

2h

m x 2
m x 2
d
d
m x
exp
exp

dx dx
2h
h
2h

m x 2
d 2
m d

x exp

2
dx
h dx
2h

2
2 2 2
2
2

m
x

m
m x
m x
m x

exp
exp

h
h
h
2h
2h
h

h2 m m 2 2 x 2
2 2
1
1
E

2
2 h
2
2m
h
h
E 12 h
2

The Harmonic Oscillator (3)

We still need to normalize it

dx e
2

m x
exp

2h

h
dx
m

m x h

Expect other solutions to have similar

behavior, at least at large x
We will guess the nature of these solutions
Multiply the wave function above by an
arbitrary polynomial P(x)

m x 2
m

0 x 4
exp

h
2h

m x 2
n x Pn x exp

2h

Pn x an x n an 1 x n 1 L a0

En n 12 h

Substitute in and see if it works

This will give you En

n=3
n=2
n=1
n=0