CHAPTER 6

Quantum Mechanics II

6.1
6.2
6.3
6.4
6.5
6.6
6.7

The Schrdinger Wave Equation

Expectation Values
Infinite Square-Well Potential
Finite Square-Well Potential
Three-Dimensional Infinite-Potential Well
Simple Harmonic Oscillator
Barriers and Tunneling
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

6.1: The Schrdinger Wave Equation

Analogous to:

dP
F
dt

The Schrdinger wave equation in its time-dependent form for a

particle of energy E moving in a potential V in one dimension is
c

The extension into three dimensions is

where

is an imaginary number.

General Solution of the Schrdinger

Wave Equation

The general form of the wave function is

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 the sine term has an imaginary number. 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

was given in the equation

The probability of the particle being between x1 and x2 is given

by

The wave function must also be normalized so that the

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

Properties of Valid Wave Functions

Boundary conditions
1)
2)
3)

4)

In order to avoid infinite probabilities, the wave function must be finite

everywhere.
In order to avoid multiple values of the probability, the wave function
must be single valued.
For finite potentials, the wave function and its derivative must be
continuous. This is required because the second-order derivative term
in the wave equation must be single valued. (There are exceptions to
this rule when V is infinite.)
In order to normalize the wave functions, they 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
,

which yields:

Now divide by the wave function:

The left side of Equation (6.10) depends only on time, and the right side
depends only on spatial coordinates. Hence each side must be equal to
a constant. The time dependent side is

Time-Independent Schrdinger Wave

Equation Continued

We integrate both sides and find:

where C is an integration constant that we may choose to be 0. Therefore

This determines f to be

free particle

This is known as the time-independent Schrdinger wave equation, and it is a

fundamental equation in quantum mechanics.

Stationary State

The wave function can be written as:

The probability density becomes:

( x)

The probability distributions are constant in time. This is a standing

wave phenomena that is called the stationary state.

Comparison of Classical and Quantum

Mechanics

Newtons second law and Schrdingers wave equation are

both differential equations.

Newtons second law can be derived from the Schrdinger

wave equation, so the latter is the more fundamental.

Classical mechanics only appears to be more precise because

it deals with macroscopic phenomena. The underlying
uncertainties in macroscopic measurements are just too small
to be significant.

6.2: Expectation Values

The expectation value is the expected result of the average of

many measurements of a given quantity. The expectation value
of x is denoted by <x>
Any measurable quantity for which we can calculate the
expectation value is called a physical observable. The
expectation values of physical observables (for example,
position, linear momentum, angular momentum, and energy)
must be real, because the experimental results of
measurements are real.
The average value of x is

Continuous Expectation Values

We can change from discrete to

continuous variables by using the
probability P(x,t) of observing the
particle at a particular x.

Using the wave function, the

expectation value is:

The expectation value of any

function g(x) for a normalized wave
function:

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:

With k = p / we have
This yields

This suggests we define the momentum operator as

The expectation value of the momentum is

Position and Energy Operators

The position x is its own operator as seen above.

The time derivative of the free-particle wave function is

Substituting = E / yields

The energy operator is

The expectation value of the energy is

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

Clearly the wave function must be zero where the potential is

infinite.

Where the potential is zero inside the box, the Schrdinger wave
equation becomes

The general solution is

where
.

Deriving the Schrodinger Equation

using operators
The energy is:

p2
E
V
2m

p2
E K V
V
2m

Substituting operators:
E:

E ih

t
2

K+V:

p2
1

i
h

V
2m
2m
x
h2 2

V
2
2m x

Substituting:

h2 2
ih

V
2
t
2m x

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 = n.

The wave function is now

We normalize the wave function

The normalized wave function becomes

These functions are identical to those obtained for a vibrating string with
fixed ends.

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:
0

Clearly the wave function must be zero where the potential is

infinite.

The energy is entirely

Where the potential is zero (inside the box), the time-independent
kinetic and so is positive.
Schrdinger wave equation becomes:

where

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 = n.

The wave function is:

We normalize the wave function:

cos(2nx/L)

A 2/ L

The normalized wave

function becomes:

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

Quantized Energy

The quantized wave number now becomes

Solving for the energy yields

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

6.4: Finite Square-Well Potential

The finite square-well potential is

The Schrdinger equation outside the finite well in regions I and III is
or using

yields

. Considering that the wave function must be zero at

infinity, the solutions for this equation are

Finite Square-Well Solution

Inside the square well, where the potential V is zero, the wave equation
becomes

where

Instead of a sinusoidal solution we have

The boundary conditions require that

and the wave function must be smooth where the regions meet.

Note that the

wave function is
nonzero outside
of the box.

Penetration Depth

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

It should not be surprising to find that the penetration distance that

violates classical physics is proportional to Plancks constant.

6.5: Three-Dimensional Infinite-Potential Well

The wave function must be a function of all three spatial coordinates.

We begin with the conservation of energy

Multiply this by the wave function to get

Now consider momentum as an operator acting on the wave

function. In this case, the operator must act twice on each
dimension. Given:

The three dimensional Schrdinger wave equation is

Degeneracy

Analysis of the Schrdinger wave equation in three dimensions

introduces three quantum numbers that quantize the energy.

A quantum state is 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.

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:

Redefining the minimum potential and the zero potential, we have
Substituting this into the wave equation:

Let

and

which yields

Parabolic Potential Well

If the lowest energy level is zero, this violates the uncertainty principle.
The wave function solutions are
where Hn(x) are Hermite
polynomials of order n.
In contrast to the particle in a box, where the oscillatory wave function is a
sinusoidal curve, in this case the oscillatory behavior is due to the polynomial,
which dominates at small x. The exponential tail is provided by the Gaussian
function, which dominates at large x.

Analysis of the Parabolic Potential Well

The energy levels are given by

The zero point energy is called the Heisenberg

limit:

Classically, the probability of finding the mass is

greatest at the ends of motion and smallest at the
center (that is, proportional to the amount of time
the mass spends at each position).
Contrary to the classical one, the largest probability
for this lowest energy state is for the particle to be
at the center.

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.
1/v

The Parabolic Potential Well

The energy levels are given by:

The zero point

energy is
called the
Heisenberg
limit:

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.
We will first consider the case when the energy is greater than the potential
barrier.
In regions I and III the wave numbers are:

In the barrier region we have

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 are
as follows:

The corresponding solutions are:

As the wave moves from left to right, we can simplify the wave functions to:

Probability of Reflection and Transmission

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

Because the particles must be either reflected or transmitted we have:

R + T = 1.
By applying the boundary conditions x , x = 0, and x = L, we arrive
at the transmission probability:

Notice that there is a situation in which the transmission probability is 1.

Tunneling

Now we consider the situation where classically the particle does not have
enough energy to surmount the potential barrier, E < V0.

The quantum mechanical result, however, is one of the most remarkable features
of modern physics, and there is ample experimental proof of its existence. There
is a small, but finite, probability that the particle can penetrate the barrier and even
emerge on the other side.
The wave function in region II becomes

The transmission probability that

describes the phenomenon of tunneling is

Uncertainty Explanation

Consider when L >> 1 then the transmission

probability becomes:

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.

Potential Well

Consider a particle passing through a potential well region rather than through a
potential barrier.
Classically, the particle would speed up passing the well region, because K = mv2 / 2 =
E + V 0.
According to quantum mechanics, reflection and transmission may occur, but the
wavelength inside the potential well is smaller than outside. When the width of the
potential well is precisely equal to half-integral or integral units of the wavelength, the
reflected waves may be out of phase or in phase with the original wave, and
cancellations or resonances may occur. The reflection/cancellation effects can lead to
almost pure transmission or pure reflection for certain wavelengths. For example, at the
second boundary (x = L) for a wave passing to the right, the wave may reflect and be
out of phase with the incident wave. The effect would be a cancellation inside the well.

Alpha-Particle Decay

The phenomenon of tunneling explains the 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
approximately 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.
According to quantum mechanics,
however, the alpha particle can
tunnel through the barrier. Hence
this is observed as radioactive decay.