Chapter 41

Quantum Mechanics
Probability – A Particle
Interpretation
 From the particle point of view, the
probability per unit volume of finding a
photon in a given region of space at an
instant of time is proportional to the
number N of photons per unit volume at
that time and to the intensity
Probability N
 I
V V
Probability – A Wave
Interpretation
 From the point of view of a wave, the
intensity of electromagnetic radiation is
proportional to the square of the electric
field amplitude, E
2
I E
 Combining the points of view gives
Probability 2
E
V
Probability – Interpretation
Summary
 For electromagnetic radiation, the probability
per unit volume of finding a particle
associated with this radiation is proportional
to the square of the amplitude of the
associated em wave
 The particle is the photon
 The amplitude of the wave associated with
the particle is called the probability
amplitude or the wave function
 The symbol is ψ
Wave Function
 The complete wave function ψ for a
system depends on the positions of all
the particles in the system and on time
 The function can be written as ψ(r1, r2, …
rj…., t) = ψ(rj)e-iωt
 rj is the position of the jth particle in the system

ω = 2πƒ is the angular frequency
 i  1
Wave Function, cont.
 The wave function is often complex-valued
 The absolute square |ψ|2 = ψψ is always real
and positive
 ψ* is the complete conjugate of ψ
 It is proportional to the probability per unit volume
of finding a particle at a given point at some
instant
 The wave function contains within it all the
information that can be known about the
particle
Wave Function, General
Comments, Final
 The probabilistic interpretation of the
wave function was first suggested by
Max Born
 Erwin Schrödinger proposed a wave
equation that describes the manner in
which the wave function changes in
space and time
 This Schrödinger wave equation represents a
key element in quantum mechanics
Wave Function of a Free
Particle
 The wave function of a free particle moving
along the x-axis can be written as ψ(x) = Aeikx
 k = 2πλ is the angular wave number of the wave
representing the particle
 A is the constant amplitude
 If ψ represents a single particle, |ψ|2 is the
relative probability per unit volume that the
particle will be found at any given point in the
volume
 |ψ|2 is called the probability density
Wave Function of a Free
Particle, cont.
 In general, the probability
of finding the particle in a
volume dV is |ψ|2 dV
 With one-dimensional
analysis, this becomes |ψ|
2
dx
 The probability of finding
the particle in the arbitrary
interval a x b is
b 2

P  ψ dx
ab
a
and is the area under the
curve
Wave Function of a Free
Particle, Final
 Because the particle must be
somewhere along the x axis, the sum of
all the probabilities over all values of x
must be 1
 2
Pab  ψ dx 1


 Any wave function satisfying this equation

is said to be normalized
 Normalization is simply a statement that the
particle exists at some point in space
Expectation Values
 ψ is not a measurable quantity
 Measurable quantities of a particle can
be derived from ψ
 The average position is called the
expectation value of x and is defined
as 
x  ψ * xψdx

Expectation Values, cont.
 The expectation value of any function of
x can also be found

f x   ψ * f x ψdx


 The expectation values are analogous to

weighted averages
Summary of Mathematical
Features of a Wave Function
 ψ(x) may be a complex function or a
real function, depending on the system
 ψ(x) must be defined at all points in
space and be single-valued
 ψ(x) must be normalized
 ψ(x) must be continuous in space
 There must be no discontinuous jumps in
the value of the wave function at any point
 Particle in a Box
 A particle is confined
to a one-dimensional
region of space
 The “box” is one-
dimensional
 The particle is
bouncing elastically
back and forth
between two
impenetrable walls
separated by L
Potential Energy for a Particle
in a Box
 As long as the particle
is inside the box, the
potential energy does
not depend on its
location
 We can choose this
energy value to be zero
 The energy is infinitely
large if the particle is
outside the box
 This ensures that the
wave function is zero
outside the box
Wave Function for the Particle
in a Box
 Since the walls are impenetrable, there
is zero probability of finding the particle
outside the box
 ψ(x) = 0 for x < 0 and x > L
 The wave function must also be 0 at the
walls
 The function must be continuous
 ψ(0) = 0 and ψ(L) = 0
Wave Function of a Particle in
a Box – Mathematical
 The wave function can be expressed as
a real, sinusoidal function
 2πx 
ψ (x )  A sin  
 λ 
 Applying the boundary conditions and
using the de Broglie wavelength
 nπx 
ψ(x )  A sin  
 L 
Graphical Representations for
a Particle in a Box
Wave Function of the Particle
in a Box, cont.
 Only certain wavelengths for the particle
are allowed
 |ψ|2 is zero at the boundaries
 |ψ|2 is zero at other locations as well,
depending on the values of n
 The number of zero points increases by
one each time the quantum number
increases by one
Momentum of the Particle
in a Box
 Remember the wavelengths are
restricted to specific values
 Therefore, the momentum values are
also restricted
h nh
p 
λ 2L
Energy of a Particle in a Box
 We chose the potential energy of the
particle to be zero inside the box
 Therefore, the energy of the particle is
just its kinetic energy
 h2  2
En  2 
n n 1, 2, 3 ,
 8mL 
 The energy of the particle is quantized
Energy Level Diagram –
Particle in a Box
 The lowest allowed
energy corresponds
to the ground state
 En = n2E1 are called
excited states
 E = 0 is not an
allowed state
 The particle can
never be at rest
Boundary Conditions
 Boundary conditions are applied to determine
the allowed states of the system
 In the model of a particle under boundary
conditions, an interaction of a particle with its
environment represents one or more boundary
conditions and, if the interaction restricts the
particle to a finite region of space, results in
quantization of the energy of the system
 In general, boundary conditions are related to
the coordinates describing the problem
Erwin Schrödinger
 1887 – 1961
 Best known as one of
the creators of quantum
mechanics
 His approach was
shown to be equivalent
to Heisenberg’s
 Also worked with:
 statistical mechanics
 color vision
 general relativity
Schrödinger Equation
 The Schrödinger equation as it applies
to a particle of mass m confined to
moving along the x axis and interacting
with its environment through a potential
energy function U(x) is
2 2
 d ψ
 2
 Uψ Eψ
2m dx
 This is called the time-independent
Schrödinger equation
Schrödinger Equation, cont.
 Both for a free particle and a particle in
a box, the first term in the Schrödinger
equation reduces to the kinetic energy
of the particle multiplied by the wave
function
 Solutions to the Schrödinger equation in
different regions must join smoothly at
the boundaries
Schrödinger Equation, final
 ψ(x) must be continuous
 ψ(x) must approach zero as x
approaches ±
 This is needed so that ψ(x) obeys the
normalization condition
 dψ/dx must also be continuous for finite
values of the potential energy
Solutions of the Schrödinger
Equation
 Solutions of the Schrödinger equation may be
very difficult
 The Schrödinger equation has been
extremely successful in explaining the
behavior of atomic and nuclear systems
 Classical physics failed to explain this behavior
 When quantum mechanics is applied to
macroscopic objects, the results agree with
classical physics
Potential Wells
 A potential well is a graphical
representation of energy
 The well is the upward-facing region of
the curve in a potential energy diagram
 The particle in a box is sometimes said
to be in a square well
 Due to the shape of the potential energy
diagram
Schrödinger Equation Applied
to a Particle in a Box
 In the region 0 < x < L, where U = 0, the
Schrödinger equation can be expressed in
the form
d 2ψ 2mE 2
2
 2
ψ  k ψ
dx 
 The most general solution to the equation is
ψ(x) = A sin kx + B cos kx
 A and B are constants determined by the
boundary and normalization conditions
Schrödinger Equation Applied
to a Particle in a Box, cont.
 Solving for the allowed energies gives
 h2  2
En  2 
n
 8mL 
 The allowed wave functions are given by

 nπx  2  nπx 
ψn (x ) A sin   sin  
 L  L  L 
 The second expression is the normalized wave function
 These match the original results for the particle in a box
Simple Harmonic Oscillator
 Reconsider black body radiation as
vibrating charges acting as simple
harmonic oscillators
 The potential energy is
U = ½ kx2 = ½ mω2x2
 Its total energy is
K + U = ½ kA2 = ½ mω2A2
Simple Harmonic Oscillator, 2
 The Schrödinger equation for this
problem is
 2 d 2ψ 1 2 2
 2
 mω x ψ Eψ
2m dx 2
 The solution of this equation gives the
wave function of the ground state as
 mω 2  x 2
ψ Be
 Simple Harmonic Oscillator, 3
 The remaining solutions that describe the
excited states all include the exponential
function 2
 Cx
e
 The energy levels of the oscillator are
quantized
 The energy for an arbitrary quantum number
n is En = (n + ½)where n = 0, 1, 2,…
Energy Level Diagrams –
Simple Harmonic Oscillator
 The brown curves
represent probability
densities for the first
three states
 The blue curves
represent the
classical probability
densities
corresponding to the
same energies
Energy Levels in the
Harmonic Oscillator
 The state n = 0 corresponds to the ground
state

The energy is Eo = ½ ω
 The state n = 1 is the first excited state
 The separations between adjacent levels are
equal and are given by E = ω
 As n increases, the agreement between the
classical and the quantum-mechanical results
improve