CHAPTER 6

Quantum Mechanics II
6.1
6.2
6.3
6.4
6.5

The Schrdinger Wave Equation

Expectation Values
Infinite Square-Well Potential
Finite Square-Well Potential
Three-Dimensional InfinitePotential Well
6.6 Simple Harmonic Oscillator
6.7 Barriers and Tunneling
Erwin Schrdinger (1887-1961)

A careful analysis of the process of observation in atomic physics has

shown that the subatomic particles have no meaning as isolated
entities, but can only be understood as interconnections between the
preparation of an experiment and the subsequent measurement.
- Erwin Schrdinger
Prof. Rick Trebino, Georgia Tech, www.physics.gatech.edu/frog/lectures

Opinions on quantum mechanics

I think it is safe to say that no
one understands quantum
mechanics. Do not keep saying
to yourself, if you can possibly
avoid it, But how can it be like
that? because you will get
down the drain into a blind
alley from which nobody has yet
escaped. Nobody knows how it
can be like that.
- Richard Feynman

Those who are not shocked

when they first come across
quantum mechanics cannot
possibly have understood it.
Richard Feynman (1918-1988)

- Niels Bohr

6.1: The Schrdinger Wave Equation

The Schrdinger wave equation in its time-dependent form for a
particle of energy E moving in a potential V in one dimension is:
2
x, t
2 x, t
i

V x, t
2
t
2m
x

where V = V(x,t)

where i is the square root of -1.

The Schrodinger Equation is THE fundamental equation

of Quantum Mechanics.

General Solution of the Schrdinger Wave

Equation when V = 0
x, t
2 2 x, t
i

Try this solution:

2m

x 2

( x, t ) Ae i ( kxt ) A[cos(kx t ) i sin(kx t )]

i Aei ( kx t ) i
t

i
(i )(i )
t
This works as long as:

k2

2m

2
2

2
x
2 2
2 2
k

2
2m x
2m

which says that the total

energy is the kinetic energy.

General Solution of the Schrdinger

Wave Equation when V = 0
In free space (with V = 0), the general form of the wave function is

( x, t ) Aei ( kx t ) A[cos(kx t ) i sin(kx t )]

which also describes a wave moving in the x direction. In
general the amplitude may also be complex.
The wave function is also not restricted to being real. Notice
that this function is complex.
Only the physically measurable quantities must be real. These
include the probability, momentum and energy.

Normalization and Probability

The probability P(x) dx of a particle being between x and x + dx is
given in the equation

P( x)dx ( x, t ) ( x, t )dx
The probability of the particle being between x1 and x2 is given by
x2

P dx

x1

The wave function must also be normalized so that the probability

of the particle being somewhere on the x axis is 1.

( x, t ) ( x, t )dx 1

Properties of Valid Wave Functions

Conditions on the wave function:
1. In order to avoid infinite probabilities, the wave function must be
finite everywhere.
2. The wave function must be single valued.
3. The wave function must be twice differentiable. This means that it
and its derivative must be continuous. (An exception to this rule
occurs when V is infinite.)

4. In order to normalize a wave function, it must approach zero as x

approaches infinity.

Solutions that do not satisfy these properties do not generally

correspond to physically realizable circumstances.

Time-Independent Schrdinger Wave Equation

The potential in many cases will not depend explicitly on time.
The dependence on time and position can then be separated in the
Schrdinger wave equation. Let:

( x, t ) y ( x) f (t )
which yields:

f (t )
2 f (t ) 2y ( x)
iy ( x)

V ( x)y ( x) f (t )
2
t
2m
x
Now divide by the wave function y(x) f(t):

1 df (t )
2 1 2y ( x)
i

V ( x)
2
f (t ) t
2m y ( x) x
The left side depends only on t, and the right side
depends only on x. So each side must be equal to
a constant. The time dependent side is:

1 df
B
f t

Time-Independent Schrdinger Wave Equation

Multiply both sides by f(t)/i:

f
B f /i
t

which is an easy differential equation to solve.

f (t ) e

Bt / i

iBt /

But recall our solution for the free particle:

ignoring the proportionality

constant, which will come from
the normalization condition

( x, t ) ei kx t

in which f(t) = exp(-it), so: = B / or B = , which means that: B = E!

f (t ) e iEt /
So multiplying by y(x), the spatial Schrdinger equation becomes:

2 d 2y ( x)

V ( x)y ( x) Ey ( x)
2
2m dx

Time-Independent Schrdinger Wave Equation

2 d 2y ( x)

V ( x)y ( x) Ey ( x)
2
2m dx
This equation is known as the time-independent Schrdinger
wave equation, and it is as fundamental an equation in quantum
mechanics as the time-dependent Schrodinger equation.

So often physicists write simply:

H y Ey

where:
2

H
V
2
2m x
2

H is an operator.

Operators

2 d 2y ( x)

V ( x)y ( x) Ey ( x)
2
2m dx

Operators are important in quantum mechanics.

All observables have corresponding operators.
The kinetic energy operator is:

2
K
2m x 2
2

Other operators are simpler and just involve multiplication.

The potential energy operator is just multiplication by V(x).
Well meet others soon.

Stationary States
The wave function can be written as:

( x, t ) y ( x )e

it

The probability density becomes:

y ( x) e y ( x) e
*

it

y ( x)

it

The probability distribution is constant in time.

This is a standing wave phenomenon and is called a stationary state.

6.2: Expectation Values

In quantum mechanics, well compute expectation values.
The expectation value, x , is the weighted average of a
given quantity. In general, the expected value of x is:

x P1 x1 P2 x2

PN xN

P x
i

If there are an infinite number of possibilities, and x is continuous:

x P( x) x dx
Quantum-mechanically:

x ( x) * ( x) x dx

* ( x) x ( x) dx

And the expectation of some function of x, g(x):

g ( x)

* ( x) g ( x) ( x) dx

Bra-Ket Notation
This expression is so important that physicists have a special
notation for it.

g ( x) * ( x) g ( x) ( x) dx

| g|

The entire expression is thought to be a bracket.

And | is called the bra with | the ket.

The normalization condition is then:

| 1

Momentum Operator
To find the expectation value of p, we first need to represent p in terms
of x and t. Consider the derivative of the wave function of a free particle
with respect to x:

i ( kxt )
[e
] ikei ( kxt ) ik
x x
With k = p / we have
This yields

p
i
x

( x, t )
p[ ( x, t )] i
x

This suggests we define the momentum operator as p i

The expectation value of the momentum is

( x, t )
p i ( x, t )
dx

.
x

Position and Energy Operators

The position x is its own operator. Done.
Energy operator: The time derivative of the free-particle wave
function is:

i ( kxt )
[e
] iei ( kxt ) i
t
t
Substituting E / yields
The energy operator is:

E[ ( x, t )] i

( x, t )
t

E i
t

The expectation value of the energy is:

( x, t )
E i ( x, t )
dx

Deriving the Schrodinger Equation

using operators
The energy is:

p2
E
V
2m

p2
E K V
V
2m

Substituting operators:
E:

E i

p2
1

V

V
2m
2m
x
2

K+V:

V
2
2m x
2

Substituting:

2
i

V
2
t
2m x

Some differential equation solutions

Consider this differential equation:

d 2y
2

k
y
2
dx

k is real

Because the constant k2 is positive, the solution is:

y ( x) Ae Be
kx

Sometimes
people use:

kx

Now suppose the differential equation is:

cosh(kx) 12 (e kx e kx )
sinh(kx) 12 (e kx e kx )

d 2y
2

k
y
2
dx

Because the constant -k2 is negative, the solution is:

y ( x) Aeikx Be ikx

or

A sin(kx) B cos(kx)

6.3: Infinite Square-Well Potential

The simplest such system is that of a particle
trapped in a box with infinitely hard walls that
the particle cannot penetrate. This potential is
called an infinite square well and is given by:

V ( x)
0

x 0, x L
0 x L

Clearly the wave function must be zero where the potential is infinite.
Where the potential is zero (inside the box), the time-independent
The energy is entirely
Schrdinger wave equation becomes:
kinetic and so is positive.

2d d2y2y ( x) 2mE
2
2
k

2
mE
/

k
y
where

V
(
x
)
y
(
x
)

E
y
(
x
)
2
2mdx 2dx 2
The general solution is:

Quantization
Boundary conditions of the potential dictate
that the wave function must be zero at x = 0
and x = L. This yields valid solutions for
integer values of n such that kL = np.

npx
y n ( x ) A sin

L
We normalize the wave function:
The wave function is:

y ( x) y n ( x) dx 1 A

*
n

The normalized wave

function becomes:

y n ( x)

cos(2npx/L)

np x
sin
dx 1 A 2 / L
L
2

2
npx
sin

L
L

The same functions as those for a vibrating string with fixed ends!

Quantized Energy
np

The quantized wave number now becomes: k n

L
Solving for the
energy yields:
p 2 2

En n 2

2mL

2mE n
2

(n 1, 2, 3,...)

Note that the energy depends on integer values of n. Hence the energy
is quantized and nonzero.
The special case of
n = 1 is called the
ground state.

p 2 2
E1
2mL2

6.4: Finite SquareWell Potential

The finite square-well potential is:

V0

V ( x) 0
V
0

x 0

Assume:
E < V0

Region I

0 x L Region II
x L

Region III

The Schrdinger equation

outside the finite well in
regions I and III is:

d 2y

V0y Ey
2
2m dx
2

d 2y 2m
2

(
V

E
)
y

y
0
2
2
dx
Considering that the wave function
must be zero at infinity, the solutions
for this equation are:

where:

2 2m(V0 E ) / 2

Region I, x 0
y I ( x) Ae x
y III ( x) Be x Region III, x L

Finite Square-Well Solution

Inside the square well, where the potential V is zero, the wave equation
2
d
y
2
2
becomes
where
(as in the infinite-well case)
k

(
2
mE
)
/

k
y
2
dx

The solution here is: y II ( x) A sin kx B cos kx Region II, 0 x L

The boundary
conditions require that: y I y II at x 0 and y II y III at x L
so the wave function
is smooth where
the regions meet.
Note that the
wave function is
nonzero outside
of the box.

The particle penetrates the walls!

The penetration depth is
the distance outside the
potential well where the
probability significantly
decreases. It is given by

2m(V0 E )

The penetration distance

is proportional to Plancks
constant.
This violates classical
physics!

6.6: Simple Harmonic Oscillator

Simple harmonic
oscillators describe
many physical
situations: springs,
diatomic molecules
and atomic lattices.

Consider the Taylor expansion of a

potential function:

1
V ( x) V0 V1 ( x x0 ) V2 ( x x0 ) 2 ...
2

Simple Harmonic
Oscillator
Consider the second-order term
of the Taylor expansion of a
potential function:

V ( x) 12 ( x x0 ) 2
Substituting this into
2 d 2y ( x)
V ( x)y ( x) Ey ( x)
Schrdingers equation:
2

2m

dx

2mE
d 2y
2m
x 2
mx 2
y 2 2 y
2 E
2
dx

2


2mE
m
Let 2 and 2 which yields:

Letting x0 = 0

d 2y
2 2

x y
2
dx

The Parabolic
Potential Well
The wave function solutions
are
where Hn(x) are Hermite
polynomials of order n.

The Parabolic
Potential Well
Classically, the
probability of finding the
mass is greatest at the
ends of motion and
smallest at the center.

Contrary to the classical

one, the largest
probability for this lowest
energy state is for the
particle to be at the
center.

Analysis of the Parabolic Potential Well

As the quantum number increases, however, the solution
approaches the classical result. This confirms the Correspondence
Principle for the quantum-mechanical simple harmonic oscillator.

The Parabolic Potential Well

The energy levels are given by:

1
1
En (n ) / m (n )
2
2

The zero point

energy is
called the
Heisenberg
limit:

1
E0
2

6.7: Barriers and Tunneling

Consider a particle of energy E approaching a potential barrier of
height V0, and the potential everywhere else is zero.
First consider the case of the energy greater than the potential barrier.
In regions I and III, the wave numbers are:
2mE
k I k III

2m( E V0 )
where V V0
In the barrier region: kII

Reflection and Transmission

The wave function will consist of an incident wave, a reflected wave, and
a transmitted wave.
The potentials and the Schrdinger wave equation for the three regions:
Region I (x 0)

V 0

Region II (0 x L)

V V0

Region III (x L)

V 0

d 2y I 2m
2 Ey I 0
dx 2
d 2y II 2m
2 ( E V0 )y II 0
dx 2
d 2y III 2m
2 Ey III 0
dx 2

All three
constants
are
negative.

The corresponding solutions are:

Region I (x 0)
Region II (0 x L)
Region III (x L)

y I Aeik x Be ik x
y II Ceik x De ik x
y III Feik x Ge ik x
I

II

II

Sines and
cosines in all
three regions

Since the wave moves from left to right, we can identify the solutions:
y I (incident) Aeik x
Incident wave
y II (reflected) Be ik x
Reflected wave
y III (transmitted) Feik x
Transmitted wave
I

Probability of Reflection and Transmission

The probability of the particle being reflected R or transmitted T is:
R
T

y I (reflected)

y I (incident)

y III (transmitted)
y I (incident)

B* B
*
AA
2

F *F
*
AA

Because the particle must be either reflected or transmitted:

R+T=1

By applying the boundary conditions

x , x = 0, and x = L, we arrive at
the transmission probability:

V0 sin ( k II L)
T 1

4
E
(
E

V
)
0

Note that the transmission probability can be 1.

Tunneling
Now we consider the situation
where classically the particle
doesnt have enough energy
to surmount the potential
barrier, E < V0.
The quantum mechanical result is one of the most remarkable
features of modern physics. There is a finite probability that the
particle penetrates the barrier and even emerges on the other side!
The wave function
in region II becomes:

y II Ce

The transmission probability

for tunneling is:

De

where

V sinh (L)
T 1 0

4
E
(
V

E
)
0

2m(V0 E )

Tunneling wave function

This violation of classical physics is allowed by the uncertainty

principle. The particle can violate classical physics by DE for a
short time, Dt ~ / DE.

Analogy with Wave Optics

If light passing through a glass prism reflects
from an internal surface with an angle greater
than the critical angle, total internal reflection
occurs. However, the electromagnetic field is
not exactly zero just outside the prism. If we
bring another prism very close to the first one,
experiments show that the electromagnetic
wave (light) appears in the second prism The
situation is analogous to the tunneling
described here. This effect was observed by
Newton and can be demonstrated with two
prisms and a laser. The intensity of the second
light beam decreases exponentially as the
distance between the two prisms increases.

Alpha-Particle Decay
The phenomenon of tunneling explains alpha-particle decay of heavy,
radioactive nuclei.
Inside the nucleus, an alpha particle feels the strong, short-range
attractive nuclear force as well as the repulsive Coulomb force.

The nuclear force dominates inside the nuclear radius where the
potential is ~ a square well.
The Coulomb force dominates
outside the nuclear radius.

The potential barrier at the nuclear

radius is several times greater than
the energy of an alpha particle.
In quantum mechanics, however,
the alpha particle can tunnel
through the barrier. This is
observed as radioactive decay.

6.5: Three-Dimensional Infinite-Potential Well

The wave function must be a function of all three spatial coordinates.
Now consider momentum as an operator acting on the wave function
in three dimensions:

p px p y pz
2

y
p xy i
x

p yy i

y
y

p zy i

y
z

So the three-dimensional Schrdinger wave equation is

2 2y 2y 2y
2 2 2 Vy Ey
2m x
y
z

or

2 2

y Vy Ey
2m

The 3D infinite potential well

Its easy to show that:

y ( x, y, z ) A sin(k x x) sin(k y y ) sin( k z z )

where:

and:

k x p nx / Lx

k y p n y / Ly

nx2 ny2 nz2

E
2 2 2
2m Lx Ly Lz

p2

When the box is a cube:

p2

2mL2

2
x

n y2 nz2

k z p nz / Lz

Degeneracy

p2

2mL2

2
x

n y2 nz2

Try 10, 4, 3 and 8, 6, 5

Note that more than one wave function can have the same energy.

The Schrdinger wave equation in three dimensions introduces

three quantum numbers that quantize the energy. And the same
energy can be obtained by different sets of quantum numbers.
A quantum state is called degenerate when there is more than
one wave function for a given energy.
Degeneracy results from particular properties of the potential energy
function that describes the system. A perturbation of the potential
energy can remove the degeneracy.