Wave Particle Duality

The electron (e-) exhibits definite mass and charge and is localized in space.
However, De Broglie proposed a wavelength associated with the electron. Further,
Davisson-Germer experiment confirms this wave behaviour by the diffraction of low
speed electrons. To help quantify this wave property of the electron, consider a beam
of monoenergetic electrons incident onto a double slit. Let a << d (a is the slit width)
Double Slit

d Electron
Detector

Electron beam
D

An electron detector is placed at a distance D >> d.

Exp. 1: Several electrons incident on the slits at the same time.

A diffraction pattern is observed on the screen.

Exp. 2 : Cover one slit

Interference pattern disappears.

Exp. 3: Reduce intensity such that one electron passes through the slit at any given
time.
What appears to be a random distribution of electons is observed on screen
initially. Over time the interference pattern is observed to develop from the random
distribution.

Exp. 2 illustrates the principle of complementarity –

Both particle and wave properties are required to describe the e-. However, they can
never be simultaneously measured. Any attempt at measuring one trait destroys the
other.
Exp. 3
The deductions here are that:
1) each e- is not interfering with the others in the beam.
2) each e- must be aware of both slits (self interference)
3) the accumulative effect of individual e- interference gives the observed
pattern.

If experiment three is repeated with photons, the results are identical to that observed
for e-‘s.

Interpretation
The photon has an electric field E (r , t ) .

A part of the field E1 passes through slit 1 while E2 passes through slit 2. They add
“vectorially”

E R (r , t ) = E1 ( r , t ) +E 2 ( r , t )

What is observed at the screen is an intensity pattern. In light the intensity is

determined by the square of the amplitude of the wave formed by superposition, i.e.

I ∝ | E R | 2 . Where the individual photon falls on screen cannot be predicted. It can

only be statistically determined. So what we have for the individual photon is a value
that tells of the probability of locating a photon within a given space/time interval.
i.e. I ( x, t ) ∝P ( x, t ) - probability of locating the photon at x, t

To Formalize the Wave Function: Born’s Interpretation

An analogy is developed by comparing the particle wave to a light wave. To describe
the wave nature of the particle – we define some distribution, the wave function (WF)
Ψ(x,t). This WF contains everything that is knowable about the e- (particle).

The interpretation of Ψ(x,t) is such that

Ψ* ( x, t ) Ψ( x, t ) dx = | Ψ( x, t ) | 2 dx = P ( x, t ) dx - Born’s Interpretation

i.e. the probability that the particle will be found in the interval dx about (x, t).

Therefore P (x,t) is a probability density.

Note:
Anything that can be known (e.g. by measurement etc.) about the particle is contained
in its WF. To ensure that the statistical nature of measurements made on Ψ(x,t) are
correctly interpreted, Ψ(x,t) must represent an ensemble of a large number of
identically prepared particles. We may loosely refer to Ψ(x,t) as the WF of a particle,
however, it must always be borne in mind that the particle is a member of the
ensemble. Further, the results obtained do not refer to one particle but is the average
result for the ensemble.
Since | Ψ(x,t) |2 ∝∝ P(x, t) to avoid any ambiguities in the predictions of the theory,

Ψ must have the following characteristics:

(i) Ψ(x,t) must be finite everywhere Ψ(x,t) ∞
(ii) Ψ(x,t) must be a single valued function.
(iii) Ψ(x,t) must be a continuous function of x and t
(iv) Ψ must possess continuous 1st and finite 2nd derivatives.

Since (in 1-D) the particle must be somewhere along the x-axis; the sum of all
probabilities over all values of x must be 1. That is
∞

∫ | Ψ( x, t ) | dx =1
2

−∞

This is referred to as the normalisation condition and any wave function satisfying
this equation is said to be normalised.

In a case where the wave function is not normalised and we have

∫ | Ψ( x, t ) | dx =C
2

−∞

then, the Normalised wave function is

1
ΨN ( x, t ) = Ψ( x, t ) .
C
We immediately see that
 ∞

∫ |Ψ
−∞
N ( x, t ) | 2 dx =1 .

Measuring Quantum Quantities

The Eigenvalue Problem
A function operator (or simple an operator) is a mathematical entity that transforms
functions into other functions. That is it has a function as its input, which it maps
uniquely to another function (output).
For an operator [Q], if the operation of [Q] on a function g, returns a multiple of the
same function, i.e.

[Q] g = λ g , where λ ∈ 

this is referred to as the eigenvalue problem. The function g is called the

eigenfunction of the operator [Q] and λ is the corresponding eigenvalue, e.g
d
Consider the mathematical operator operating on the function e αx
dx
d αx
We have e = α e α x . Clearly e αx is an eigenfunction of the operator with
dx

eigenvalue α.

Notation: a commonly used notation for operators is Q( = [Q])

Quantum Operators and Expectation Values

An observable is any particle property that can be measured (e.g. position, kinetic
energy, momentum, etc.)
Quantum mechanics associates an operator with every observable.

Examples of Quantum Mechanical Operators

Observable Symbol Associated Operator

Position [x] x
Momentum [p] h d
i dx
Kinetic Energy [K] h ∂2
−
2m ∂x 2
Hamiltonian [H] h ∂2
− +V ( x)
2m ∂x 2
Total Energy [E] ∂
ih
∂t

The eigenvalue problem in quantum mechanics determines the value obtained for
measured quantities. For example, take the equation
[ H ]ψ( x ) = E ψ( x )

It says that the Hamiltonian operation on this wave function returns an eigenvalue E.
This eigenvalue is the measurement of the observable represented by the operator; in
this case energy.

The Expectation Value is the value of an observable one would obtain, from
measurements of the observable made on a large number of particles with the same
WF (ensemble).
If the eigenfuction of an ensemble of particles is known, it may be used to calculate
the average value that one would obtain when repeated measurements of that
observable are made on the system. For observable Q the expectation value, denoted
as <Q> is given by
∞
Q = ∫ Ψ* ( x, t ) [Q ] Ψ( x, t ) dx
−∞

where Ψ (x,t) is the normalised eigenfunction of the operator [Q]

Quantum Uncertainty
This measures the inherent spread in the results of measurements of an observable
about the expectation value. The uncertainty in an observable with operator [Q] is
given by

∆ Q = < Q2 > − < Q > 2

If ∆ Q is zero, then the observable Q is said to be sharp. That is, every measurement
of Q made on the ensemble yields the same value. Thus there is no spread or
distribution in the measurement.
Operator Algebra
Quantum operators follow the general algebra
([Q] + [P]) Ψ = [Q] Ψ + [P]Ψ
[Q] Ψ + [P]Ψ = [P] Ψ + [Q]Ψ
[Q] aΨ = a[Q] Ψ, a0 
[Q][P] Ψ = [ Q] ([P] Ψ)
however
[Q][P] Ψ ≠ [ P] ([Q] Ψ), they do not necessarily commute; so the order is
important.

Schrödinger Equation (SE)

Quantum mechanics is concerned with the evolution of the wave function in time.
That is given Ψ(x,0) we wish to determine Ψ(x,t). The equation that governs this
evolution is the Schrödinger equation
2
∂2 ∂
− Ψ( x, t ) +V ( x ) Ψ( x, t ) =i Ψ( x, t )
2m ∂x 2
∂t

Solution to this 2nd order partial differential equation may be obtained by method of
separation of variables:

We assume that the solution to the equation may be separated into a function of x and
a separate function of t i.e.

Ψ(x,t) = ψ(x) ϕ(t)

If this is substituted into (S.E.) we have

2
− ψ" ϕ(t ) +V ( x )ψ( x ) ϕ(t ) =iψ( x ) ϕ
 (t )
2m
 df df
f ′= f =
dx dt

divide the resulting equation by ψ(x) ϕ(t) leading to

2
ψ" ϕ
 (t )
− +V ( x ) =i
2m ψ ϕ(t )
Since the LHS and RHS both hold for any value of the independent variables x and t,
then they must both be equal to the same constant. Call this constant E

ϕ

∴i =E
ϕ
or
dϕ
i =Eϕ a first order differential equation
dt
with solution
ϕ =ϕ0 e −iEt / 

and the second equation

−  2 d 2ψ
+ V ( x)ψ ( x ) = Eψ ( x )
2m dx 2

This second equation is called the Time Independent S.E. (TISE) and may be solved
for a given V(x).

E – the constant has dimensions of energy and is taken to be the total mechanical
energy.
Free Particle (An exact solution to S.E.)
The free particle has potential
V(x) = 0 everywhere
- dV(x)
Since F(x) = , then a free particle has no forces acting on it. If we
dx
substitute for this potential into the TISE we see that this equation for the free particle

−  2 d 2ψ ( x)
is = Eψ ( x )
2m dx 2
Which can be rearranged to give

d 2ψ − 2m
2
= Eψ
dx 2

d 2ψ 2mE
⇒ + k 2ψ = 0 where k2=
dx 2
2

The general solution to this 2nd order differential equation is

ψ( x ) = A′e ikx + B ′e −ikx

Since the wave function Ψ(x, t) was assumed separable i.e.

Ψ(x, t) = ψ(x) ϕ(t)
Then we have both terms
ψ( x ) = A′e ikx + B ′e −ikx
And
ϕ(t ) =ϕ0 e −iEt /
(from above)

hence, the wave function for the free particle

Ψ( x, t ) =( A′ e ikx + B ′ e −ikx ) ϕ0 e −iEt /

which may be rewritten as

E E
i ( kx − t) −i ( kx + t)
Ψ( x, t ) = A e 
+B e 

If we let E/ħ = w then

 Ψ( x, t ) = A e i ( kx −wt ) +B e −i ( kx +wt )

Hence we see that the wave function of a free particle is the super position of waves
travelling in opposite directions. If it is given that the particle is travelling in the +x
direction then B = 0 and
i ( kx −wt )
Ψ( x, t ) =Ae

To Be Continued