Section 1.

The concepts and postulates of

quantum mechanics
Set up formal approach to quantum theory,
based on a series of postulates
Discuss wavefunctions, operators, eigenvalues
and eigenfunctions
Show how we can predict the results of
measurements of a quantum system
Discuss the uncertainty principle
Discuss the time dependence of quantum
systems

1.1 Postulate 1
The state of a quantum system is completely
defined by its wavefunction . Everything we
can know about the system can be derived from
.
One particle in one dimension: ( x, t )
One particle in three dimensions: ( r , t )

Two particles in three dimensions: r1 , r2 , t

In general, is a complex function. The

probability P of finding a particle at a point in
2
space is proportional to .
2

1 particle in 1-D: P ( x, t )dx = ( x, t ) dx

2

1 particle in 3-D: P ( r , t )dr = ( r , t ) d r

3

Cartesians:

d 3r = dx dy dz

Spherical polars:

d 3r = r 2 sin dr d d

Wavefunctions are normalised:

( x, t ) dx = 1
1 particle in 3-D: ( r , t ) d r = 1

1 particle in 1-D:

Integrate over the region of space available to

the particle

1.2 Postulate 2
Every measurable quantity (observable) has a
corresponding operator.
Operators are mathematical rules that act on
a function to give another function, eg

A f ( x) = g ( x)
Examples
Let f ( x) = x + x 2

Differential operator: A =
g ( x) = 1 + 2 x
dx
Multiplicative operator: A = x 2 g = x3 + x 4
Parity operator: A f ( x) = f ( x) g = x + x 2

Products of operators are defined as

f ( x) = A ( B ( f ( x)))
AB
The order of operators is important:

is not necessarily BA

AB
In general, A and B do not commute
Example
Let f ( x) = x + x ,
2

A = d , B = x
dx

A A f ( x) = A 2 f ( x) = 2
f ( x) = 2 x + 3x 2
AB
f ( x) = x + 2 x 2
BA
BA
in this case
AB

Operators in quantum mechanics are linear and

Hermitian.
Linear: A (c1 f1 + c2 f 2 ) = c1 A f1 + c2 A f 2
( c1 , c2 are constants, f1 , f 2 are functions)
Hermitian:

( x) dx = A f ( x) f ( x) dx
f ( x) Af
2
2
1

(integrate over region available to the particle)

Some important operators
Position: x = x,
Momentum:

p x = i ,
x

y = y, z = z ie r = r

p y = i ,
y
ie p = i

p z = i
z

Other operators are derived from these and the

classical definitions:

1 2 p2
Kinetic energy, classically T = mv =
2
2m
2
2

p
2

in QM: T =
=

2m
2m

Potential energy: V ( r ) = V ( r )
Total energy (ie Hamiltonian): H = T + V

H
H

2 2
=
+V (r )
2m
2
2

=
+ V ( x)
2
2m x

in 3D
in 1D

Check that these operators are Hermitian

( x) dx = A f ( x) f ( x) dx
f ( x) Af
2
2
1

Position operator: A x = x
Multiplicative operator is obviously Hermitian

Momentum operator: A p x = i
x

f 2 ( x)
f ( x) ( p x f 2 ( x) ) dx = i f ( x)
dx
x

Integrate by parts

f1
f1
i
f 2 ( x ) + i
f 2 ( x) dx
x
x

Assume functions are well behaved at the

boundaries of the region

f
i
f 2 ( x) dx = ( p x f1 ) f 2 ( x) dx Hermitian
x
For kinetic energy see problems sheet

1.3 Postulate 3
The only possible result of a measurement is an
eigenvalue of the relevant operator. Whatever
the state of the system before the measurement,
the state immediately after is the corresponding
eigenfunction.
Eigenvalues and eigenfunctions
the equation
For a general operator A,

A =
(with relevant boundary conditions) has nonzero solutions only for special values of . We
write these solutions as

A n = nn

n are the eigenvalues of A

n are the eigenfunctions of A
The label n can be discrete or continuous

Examples

Momentum operator in 1D: p x = i

x

i exp(ikx) = k exp(ikx)
x
Eigenvalues: k (where k is a constant)
Eigenfunctions: exp(ikx)
In this case, the eigenvalues are continuous
Physical interpretation: the wave exp(ikx)
represents a particle moving in the x direction
with a momentum p = k

h
(Consistent with de Broglie relation = )
p
If we measure the momentum of a quantum
particle we obtain a value p = k and
immediately after the measurement the
wavefunction is = exp(ikx)

Infinite square well

Potential energy V ( x) = 0 for 0 < x < a and is
infinity elsewhere
Total energy operator in the region available to
the particle:
2
2

H =
2m x 2

Eigenvalues and eigenfunctions given by:

n x n
n x

sin
si n
=

2
2
2m x
2
a
ma
a

2 2

2 2 n 2
Eigenvalues: En =
( n is an integer)
2
2ma

n x
Eigenfunctions: n ( x) sin

a
In this case, the eigenvalues are discrete

If we measure the energy of a particle in an

infinite square well, the result will be one of the
eigenvalues En . Immediately after the
measurement the wavefunction is = n ( x) .

As a result of the measurement, the

wavefunction collapses into one of the
eigenfunctions.
Quantum Measurement Problem

1.4 Properties of Hermitian operators

Start with

An = nn
Multiply both sides by m and integrate over
relevant range:

An = n mn

Because A is Hermitian, this becomes:

Am n = n mn

Taking complex conjugate of Am = mm gives

A = , so (1) becomes:

( )
m

m m

m n

=0

If n = m , then n = n so n is real
If n m , then mn = 0 so s are orthogonal
If eigenfunctions are normalised we can write

mn = mn

The eigenvalues of Hermitian operators are real

and the eigenfunctions corresponding to
different eigenvalues are orthogonal
The eigenfunctions of Hermitian operators
form a complete set, so that any function (in the
relevant region of space) can be written as a
linear combination:

F = c11 + c22 + = cnn

n

We have assumed that there is no degeneracy

(ie that all eigenvalues are different).
Everything works OK if there are degenerate
eigenvalues.

1.5 Postulate 4
Quantum mechanics is not deterministic. We
can only predict the probability of the result of
a measurement and the average over a series of
measurements.
How do we calculate these probabilities?
Assume we make a measurement, where the
sets of eigenvalues and eigenfunctions of the
corresponding operator A are { n } and {n }
At the time of the measurement the normalised
wavefunction of the system is
We can write = cnn
n

The probability of measuring m (and

2
collapsing the system into m ) is cm

Because and {n } are normalised:

How can we find the coefficents cm ?

Start with:

= cnn
n

Multiply both sides by m and integrate

=
c

m n mn
n

Use orthogonality

= c

mn

= cm

cm = m
cm gives the amount of m contained in

=1

Example: Infinite square well in 1-D

Suppose wavefunction is constant at the time of
the measurement

1
( x) =
a
We measure the total energy of the particle; the
corresponding eigenvalues and eigenvectors are

2 2 n 2
En =
2ma 2

2
n x
n ( x) =
sin

a
a

The coefficients are:

2
cm = =
a

m x
0 sin a dx
a

2 2
cm =
for m odd
m
cm = 0 for m even


8
Probability of measuring E1 =
is 2
2
2ma

4
is 0
Probability of measuring E2 =
2
2ma
2

9
8
Probability of measuring E3 =
is
2
2ma
9 2
2

Expectation values
Suppose we have a large number of identical
systems. What would be the average value of a
measurement taken on each these systems?
Average, or expectation value of the
measurements with corresponding operator A
2

A = cn n
n

This can be expressed in a more useful form

A = A
Show that these are equivalent:
A = ( cm m )A ( cnn )

= ( cm m )( cn nn )

= cm cn n mn
m

= cn n
2

Note that all our analysis has assumed that the

eigenvalues are discrete. Everything works OK
if the eigenvalues are continuous.

Expectation value of position:

x = x dx
Expectation value of momentum:

p x = i
dx
x