Lecture #3

Today’s Program:
1. Review of previous lecture
2. QM free particle and particle in a box.
3. Principle of spectral decomposition.
4. Fourth Postulate

Math tools covered today

1. Learn how to solve separable differential equations.
2. A basis of functions, how to expand a function in terms of a set of basis functions
3. Inner products (dot product in vectors) in function space.
4. A basis of functions, how to expand a function in terms of a set of basis functions
5. The connection between symmetries in the physical system, invariance of the
Hamiltonian and conserved physical quantities (this is one of the underlying
themes in this course to be expanded on in future lectures)

Questions you will by able to answer by the end of today’s lecture

1. How to find statevectors (wavefunctions) for two simple yet important cases.
2. Learn how to verify that a given statevector is an eigenvector (eigenfunction) of
an operator.
3. Find the spatial and temporal solutions of Schroedinger’s equation for a system
which is described by a time independent Hamiltonian (no explicit time
dependence of the Hamiltonian).
4. Show that the spatial solution is in fact an eigenfunction of the Hamiltonian.
5. Show how spatial confinement of the system leads to energy discretization.
6. Know the qualitative differences between the free particle case and the particle in
a box.
7. What is the condition that leads to energy discretization?
8. How to find the projection of a function (vector) onto an eigenfunction (element
of the basis)
9. How to expand an arbitrary wavefunction in terms of eigenfunctions?
10. How to predict the probability of obtaining a particular measurement result.
First Example: The Hamiltonian of a free particle:
r r
p2 P2
H classical = →H =ˆ
2m 2m
r r
P⋅P h r h r  ∂ ∂ ∂  ∂ ∂ ∂ 
H=
ˆ = ∇ ⋅ ∇ = − h 2  xˆ + yˆ + zˆ  ⋅  xˆ + yˆ + zˆ 
2m i i  ∂x ∂y ∂z   ∂x ∂y ∂z 
focus on a 1D problem for simplicity:
To find the eigenfunctions u ( x, t ) of a particular operator one needs to solve the

following equation:
ˆ ( x, t ) = λ u ( x, t )
Au

The eigenvalues of the Hamiltonian operator are called the energy let us now find an
eigenfunction for the operator which we have called the Hamiltonian.
Note: we will use the symbol u for a eigenfunction.
ˆ ( x, t ) = Eu ( x, t )
Hu

h2 ∂ u ( x ) ∂ 2 u ( x ) 2m
2

− = Eu ( )
x → + 2 Eu ( x ) = 0
2m ∂x 2 ∂x 2 h
2m 2m
i Ex −i Ex
u E ( x ) = ae h2
+ be h2

So we have now the energy eigenfunctions and energy eigenvalues for the free particle
case. Please note that these functions are oscillating and spread over all space and that E
can assume any value positive or equal to zero.
The sixth postulate allows us to find the time evolution of a state using the Schrodinger
equation.

h 2 ∂ ψ ( x, t ) ∂ψ ( x, t )
2

− = i h
2m ∂x 2 ∂t
This equation is a partial differential equation, which can be solved using a separation of
variables method:
ψ ( x, t ) = φ ( x ) ξ ( t )

substituting in the above equation gives,

h2 1 d φ ( x ) 1 dξ ( t )
2

− = ih =E
2m φ ( x ) dx 2
ξ ( t ) dt
The time dependent part becomes:
dξ ( t ) E E
−i t
+i ξ (t ) = 0 → ξ (t ) = e h
dt h
The spatial part becomes,

∂ 2φ ( x ) 2m
+ Eφ ( x ) = 0 → φ ( x ) = ae + ikx + be−ikx = u E ( x )
∂x 2
h 2

2m
k= E
h2
Each distinct E corresponds to a different valid solution which has the form:
E

( )e
−i t
ψ E ( x, t ) = ae + ikx
+ be − ikx h

so the complete solution can be written as a superposition of the individual solutions:

Ei

( )
N −i
ψ ( x, t ) = ∑ ai e + iki x + bi e− iki x e
t
h

i =1
Second example: particle in an infinite potential well:
I] The system:
A particle of mass 2m in a potential well:

II] The classical energy function of the system:

p2
H ( x, p ) = +V ( x)
2m
where the potential energy is defined as follows
 d d
 0 − <x<
V ( x) =  2 2
∞ d d
x < − or x >
 2 2
III] Obtaining the QM Hamiltonian operator:

h2 ∂ 2
( )
H ( x, p ) → Hˆ Xˆ , Pˆ =
Pˆ 2 ˆ ˆ
2m
( )
+V X = −
2m ∂x 2
+V ( x)

where,
 d d
 0 − <x<
V ( x) = 
2 2 .
∞ d d
x < − or x >
 2 2
For the moment let us restrict our attention to the region of space which has a finite
potential and consider the possible eigenfunctions and eigenvalues of the operator:
h2 ∂ 2
( )
Hˆ Xˆ , Pˆ = −
2m ∂x 2

IV] What are the energy eigenfunctions and eigenvalues?

h2 ∂ 2
ˆ ˆ( ˆ )
H X , P u ( x ) = Eu ( x ) → −
2m ∂x 2
u ( x ) = Eu ( x )

h2 ∂ u ( x ) ∂ 2 u ( x ) 2m
2

− = Eu ( x ) → + 2 Eu ( x ) = 0
2m ∂x 2 ∂x 2 h
2m 2m
i Ex −i Ex
u E ( x ) = ae h2
+ be h2

Note: The undetermined a and b coefficients imply that there are an inifinite number of
allowed eigenfunctions corresponding to every eigenvalue (i.e. determining E does not
determine a and b). We will narrow down this set by using boundary conditions derived
from physical insights into our problem. Specifically, we will require that our
eigenfunctions will be equal to 0 at the boundary of the well. At the moment we do not
have a solid justification for this other than the definition of the problem which is such
that the wavefunctions need to be equal to zero at the boundaries and therefore we want
to choose a basis set which can be conviently used to express the wavefunctions.
The problem of finding the eigenfunctions and eigenvalues of a linear quantum
mechanical operator basically is identical to solving a linear differential equation. As
such we can apply the techniques and theories which have been developed to solve
differential equations to our problems.
A differential equation of the type we are considering will have a unique solution
provided that the values of the solution are known at the boundaries (boundary
conditions).
The boundary conditions in this problem are:
 d
u x = ±  = 0
 2

 d   + ik 2 − ik   kd   kd 
d d
kd kd
u   =  ae + be 2  = 0 → a  cos + i sin  + b  cos − i sin  = 0
2    2 2   2 2 
kd kd
→ ( a + b ) cos + ( a − b ) sin =0
2 2
→a=b
kd π
→ = n n=1,3,5 ....
2 2
or
a = −b
kd π
= n n=2,4,6 ....
2 2

The form of the solution is,

 nπ x
 n odd c cos kn x = c cos d
u E ( x ) ≡ un ( x ) = 
n even d sin k x = d sin nπ x
 n
d
2mEn nπ
kn = =
h2 d

h2 ∂2 h 2 kn
( )
2
Hˆ Xˆ , Pˆ ψ ( x ) = − a cos k x = a cos kn x = En a cos kn x = Enψ ( x )
2m ∂x 2
n
2m
( )
Hˆ Xˆ , Pˆ u ( x ) = E u ( x )
n n n

Because H is a linear operator any superposition of solutions is also a solution.

The boundary conditions have lead to a quantization of the energy levels:

kd π
=n n=1,2,3,4,5....
2 2
1  nπ h 
2
n2h2
→ En =   =
2m  d  8md 2

V] Finding Schrodinger’s equation and the wave function:

∂ h2 ∂2 ∂
( )
Hˆ Xˆ , Pˆ ψ ( x, t ) = ih ψ ( x, t ) → −
∂t 2m ∂x 2
ψ ( x , t ) = ih ψ ( x , t )
∂t
We have already solved this equation and the solutions are:
E

( )
−i t
ψ ( x, t ) = ae + ikx + be −ikx e h

2mE
k=
h2
Let us focus on the spatial component:

(
ψ ( x ) = ae + ikx + be − ikx )
note: ψ ( x ) is not the complete wave function!

Where c, d are some normalization constant.

How do we normalize a vector basis cvi ?

vi 1
→c=
( vi , vi ) ( vi , vi )
The constant therefore is

→ c 2 = ( un ( x ) , un ( x ) )
1 −1
c=
(u ( x ) , u ( x ))
n n

nπ x
d /2
1 d 2
2
= ∫ cos 2 dx = → c =
c −d / 2
d 2 d
using:
1
cos 2 x = (1 + cos 2 x )
2
1
sin 2 x = (1 − cos 2 x )
2
  2nπ x  
d /2 2
cn
∫
−d / 2
2  1 + cos  d   dx = 1
  
 2nπ x 
d /2 2 d /2 2
cn c
∫ 2
dx + ∫ n cos 
2  d
 dx = 1
3
1424
−d / 2
3 −1444
d /2
424444
cn 2 d =0
=
2

2
cn2 =
d
Discussion:
Comparison between the eigenvalues and eigenvectors of the free particle and particle in
a box. One has continuous spectrum the other is discrete. The discrete character was a
result of the boundary conditions – the fact the particle was confined to a particular
region in space.

Free particle Particle in a box

 nπ x
Hamiltonian  n odd c cos kn x = c cos d
uk ( x ) = eikx un ( x ) = 
eigenfunctions n even d sin k x = d sin nπ x
 n
d
Hamiltonian h 2k 2 h2k 2 nπ
Ek = En = ,k=
eigenvalues 2m 2m d
Points to emphasize:
1. discrete vs. continuous spectrum
2. dependence of energy level separation on size of well.
3. number of nodes vs. energy of eigenfunction
4. solutions are either odd or even
5. lowest energy solution is even
Principal of spectral decomposition
Consider a system whose state is characterized at a given time by the wavefunction
r
ψ ( r , t ) . We want to predict the result of a measurement at this time of a physical

quantity a associated with the observable A. The prediction of a possible outcome will
be in terms of probabilities. We will now give a set of rules which allow us to predict the
probability of obtaining in a measurement any eigenvalue of A.

Let us first assume that the spectrum of A is entirely discrete. If all the eigenvalues an of

A are non-degenerate there is associated with each of them a unique eigenvector un ( x ) :

ˆ ( x) = a u ( x)
Au n n n

Since A is Hermitian the set of un ( x ) is a basis in the wavefunction space. That means

that any wave function,

r
ψ ( r , t ) = ∑ cnun ( x, t )
n

Defined an inner product between two functions

ϕ ( x ) ψ ( x ) = ∫ ϕ ( x ) ψ ( x ) dx
•

Remind ourselves of the geometrical interpretation (in 2D for simplicity)

Look at two vectors ψ , ϕ (psi and phi), the inner product results in a number (could be
complex scalar) tells us what the projection of one on the other is. Now the projection is
independent of the basis which you decide to represent your vector in.
ϕ ψ =c

how do we represent a vector ψ in a particular basis:

we choose a particular set of vectors which span the vector space ϕ1 , ϕ 2 usually we
choose basis set to be orthonormal.
then we find the projection of ψ in the direction of each basis vector.

ϕ1 ψ = c1
ϕ 2 ψ = c2
 Write the original function as a linear combination of the basis vectors.
ψ = c1ϕ1 + c2ϕ 2
In general
N
ψ = ∑ ciϕi
i =1

Finding the eigenvectors and eigenvalues of operators, discuss the geometrical

interpretation of eigenvectors and eigenvalues – scaling.

Example: Particle of mass m in an infinite potential well

We saw that the eigenfunctions are of the form:
 2 2 nπ x
 n odd cos kn x = cos
 d d d
un ( x ) = 
n even 2 2 nπ x
 sin kn x = sin
d d d
2mEn nπ
kn = =
h2 d
Suppose you had now a wave function
d3 d 2 d2
ψ ( x) = − x − x + x3
8 2 4

1.4

1.2

0.8

0.6

0.4

0.2

0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1

Could you express it in terms of your eigenfunctions?

 105  d 3 d 2 d 2  2 nπ x 2 nπ x
ψ ( x) = 7 
− x − x + x3  = ∑ an cos + ∑ bn sin
d  8 2 4  n d d n d d

Fourth Postulate (discrete non-degenerate): When the physical quantity a is measured

on a system in the normalized state ψ ( t ) the probability P ( an ) of obtaining the non-

degenerate eigenvalue an of the corresponding observable is

P ( an ) = un ψ = ( un ( x ) ,ψ ( x ) )
2 2

where un ( x ) is the normalized eigenvector of A associated with the eigenvalue an .