The foundations of quantum mechanics

The whole of quantum mechanics can be expressed in terms of a small set of

postulates. When their consequences are developed, they embrace the
behaviour of all known forms of matter, including the molecules, atoms, and
electrons that will be at the centre of our attention in this book.

have seen the Schrödinger equation written in the form

Hˆ (q )ψ n (q ) = Enψ n (q )
 2 d 2ψ ( x )
− 2
+ V( x )ψ ( x ) =
Eψ ( x )
2m dx

 2 d 2 
− 2
+ V( x ) ψ ( x ) =
Eψ ( x )
 2m dx 

Operator
1
The foundations of quantum mechanics
An operator is a rule that transforms a given function into
another function.

Observable any dynamical variable that can

be measured.

Hermitian linear operator Real dynamical variable –

represents observable quantity

Eigenfunction A state associated with an

observable

Eigenvalue Value of observable associated

with a particular linear operator
and eigenfunction
2
Linear Operators
ψn represent states of a dynamical system, s, p, d, etc states of H atom.
Need math relations to work with ket vectors to obtain observables.

Linear operators
The operators we shall meet in quantum mechanics are all linear. A linear
operator is one for which:
ˆ ( af ( x ) + bg ( x ) ) = aΩ
Ω ˆ f ( x ) + bΩ
ˆ g( x )
ˆ ( cf ( x ) ) =
Ω cΩ
ˆ f ( x)

where a, b and c are constants and f(x) and g(x) are functions.

A linear operator is completely defined when its application to every

eigenfunction is known.

Examples of linear operators include:

2
d
xˆ 2 , 2
, ...etc 3
dx
Linear Operators
Is d/dx a linear operator? Is a linear operator?

ˆ ( af ( x ) + bg ( x ) ) = aΩ
Ω ˆ f ( x ) + bΩ
ˆ g( x )
ˆ ( cf ( x ) ) =
Ω cΩ
ˆ f ( x)

Lets check it
d df dg d d
( f ( x ) + g( x ) ) = + = f ( x ) + g( x )
dx dx dx dx dx
Linear Operator
d df ( x ) d
(=cf ( x ) ) c= c f ( x)
dx dx dx

f ( x ) + g( x ) ≠ f ( x ) + g( x ) nonlinear Operator

4
Rules about linear operators

Additive and Subtractive

{αˆ ± βˆ } f ( x ) =αˆ f ( x ) ± βˆ f ( x )

Multiplication - associative

αβ
ˆ ˆ } f ( x ) αˆ=
{= { βˆ f ( x )} αβ
ˆ ˆ f ( x)

we first operate on with the operator on the right of the operator product,
and then we take the resulting function and operate on it with the operator
on the left of the operator product.

Multiplication is NOT necessarily commutative

αβ
ˆ ˆ f ( x ) ≠ βα
ˆ ˆ f ( x ) in general

5
Rules about linear operators

Multiplication is NOT necessarily commutative

αβ
ˆ ˆ f ( x ) ≠ βα
ˆ ˆ f ( x ) in general

�
For example, consider the operators d/dx and 𝒙𝒙
d
Dxf ( x ) =
ˆ ˆ
dx
[ ˆ ( x )]
xf

= f ( x ) + xf ´( x )

= (1ˆ + xD
ˆ ˆ ) f ( x)

ˆ ( x ) = xˆ  d f ( x ) 
ˆxDf  dx 
 
= xf ´( x )
6
Rules about linear operators

Operators obey the associative law of multiplication

αˆ  βγ
ˆ ˆ  f ( x ) = αβ

ˆ ˆ  γˆ f ( x )
 

�
For example, consider the operators d/dx and 𝒙𝒙

A major difference between operator algebra and ordinary algebra is that

numbers obey the commutative law of multiplication, but operators do not
necessarily do so

ab = ba if a and b are numbers

but
αβ
ˆ ˆ and βα
ˆ ˆ are not necessaarily equal operator

7
Commutator of Linear Operators
 Aˆ , B
ˆ  AB
= ˆ ˆ − BA
ˆˆ (This implies operating on an arbitrary eigenfunction)
 
If A and B numbers, = 0

Operators don’t necessarily commute.

ˆ ˆ f ( x ) = Aˆ  Bˆ f ( x ) 
AB  
= Aˆ [ h( x )]
= g( x )

ˆ ˆ f ( x ) = Bˆ  Aˆ f ( x ) 
BA  
= Bˆ S ( x )
= T ( x)

In General
g( x ) ≠ T ( x ) A and B do not commute.
8
If ˆ ˆ = BA
AB ˆˆ
 Aˆ , Bˆ  = AB
ˆ ˆ − BA
ˆˆ=0
 
then A ˆ and Bˆ commute.
Only know what an operator does by operating on a eigenfunction.

ˆ ˆ = BA
AB ˆˆ really means

=
ˆˆ
AB f= ˆ ˆ ( x)
( x ) BAf

ˆ ˆ = BA
AB ˆˆ is a short hand. It does not mean the right and left hand sides
of the equation are equal algebraically.

It means ˆ ˆ and BA
AB ˆˆ
have the same result when applied to an arbitrary ket. 9
Have algebra involving linear operators.

1. associative law of multiplication holds

2. distributive law holds

3. commutative law does not hold

4. Useful identities in linear-operator manipulations are

( Aˆ + Bˆ ) Cˆ =AC
ˆ ˆ + BC
ˆˆ

Aˆ ( Bˆ + Cˆ ) = AB
ˆ ˆ + AC
ˆ ˆ

Assume: The linear operators correspond to the

dynamical variables of a physical system. 10
Eigenfunctions and Eigenvalues.

Suppose that the effect of operating on some function f(x) with the linear
operator 𝑨𝑨� is simply to multiply f(x) by a certain constant k. We then say
� with eigenvalue k. (Eigen is a German word
that f(x) is an eigenfunction of 𝑨𝑨
meaning characteristic.)

ˆ ( x ) = kf ( x )
Af

As an example, e2x is an eigenfunction of the operator d/dx with eigenvalue 2

 d  2x
 dx  e = 2 e 2x

 

Lets do some work…. Is the function cos(3x+5) an eigenfunction of the

operator d2/dx2 and, if so, what is the corresponding eigenvalue?

11
 Operators and Quantum Mechanics

Eigenvalues and Eigenvectors

Hˆ ψ n = Enψ n
linear operator Function number (real) same Function

Eigenvalue problem (Mathematical problem in linear algebra.)

 2 d 2 
− 2
+ V( x ) ψ ( x ) =
Eψ ( x )
 2m dx 

we see that the Schrödinger equation is an eigenvalue problem. The values of

the energy E are the eigenvalues. The eigenfunctions are the time-
independent wave functions ψ. The operator whose eigenfunctions and
eigenvalues are desired is called the Hamiltonian operator for the system.
12
Dynamical Variables
coordinates
components of velocity
momentum
angular momentum
energy
etc.

Linear Operators ⇒ Questions you can ask about a system.

For every experimental observable, there is a linear operator.

Q. M. dynamical variables not subject to an algebra in which

the commutative law of multiplication holds.

Consequence of Superposition Principle.

(Will lead to the Uncertainty Principle.)
13
Observables and Linear Operators

Eigenfunctions State of dynamical system.

Linear operators Dynamical variables.

Question you can ask about the state of a system.

Observables Real Dynamical Variables.

Observables are the eigenvalues of Hermitian Linear Operators.

Hermitian operators Real Dynamical Variables.

14
Observables ⇒
Eigenvalues of Hermitian Operators (real eigenvalues)

Hˆ ψ n = Enψ n
linear operator observable value

eigenvector
eigenket

For every observable there is a linear operator

(more than one form).
The eigenvalues are the numbers you will measure
in an experiment.

15
 Operators and Quantum Mechanics
Hˆ ψ n = Enψ n
For a system where the potential energy is a function of the coordinates
only, the total energy remains constant with time; that is, E is conserved.
We shall restrict ourselves to such conservative systems.
The construction of operators

Operators for other observables of interest can be constructed from the

operators for position and momentum.

1. Write the classical expression for the observable in terms of position

coordinates and the linear momentum.
∂  ∂
1. Replace q by multiplication by q, and replace Pq by Pˆq =
−i =
(and likewise for the other coordinates). ∂q i ∂q

16
 Operators and Quantum Mechanics
Let us find the classical-mechanical Hamiltonian function for a particle of
mass m moving in one dimension and subject to a potential energy V(x)

The Hamiltonian function is equal to

H= K + V ( x )
1
= mv 2 + V ( x )
2
We know =
that Px =
mv x , Py mv y =
and Pz mv z
We can write
Px 2
H = + V ( x)
2m
In Q.M., The operators for the components of linear momentum are
 ∂  ∂  ∂
=Pˆx = , Pˆ y = , Pˆz ,
i ∂x i ∂y i ∂z 17
 Operators and Quantum Mechanics
Let us find the classical-mechanical Hamiltonian function for a particle of
mass m moving in one dimension and subject to a potential energy V(x)

The Hamiltonian function is equal to

H= K + V ( x )
1
= mv 2 + V ( x )
2
We know =
that Px =
mv x , Py mv y =
and Pz mv z
We can write
Px 2
H = + V ( x)
2m ∂  ∂
Pˆq =
−i =
∂q i ∂q
In Q.M.  2
∂ 2
Hˆ = − + V ( x) ∂ 2

2 m ∂q 2 Pˆq = Pˆq Pˆq = − 

2 2

∂18
q2
 Operators and Quantum Mechanics

How are the quantum-mechanical operators related to the corresponding

properties of a system? Each such operator has its own set of eigenfunctions
and eigenvalues.

Hˆ ψ n = Enψ n

The operator 𝑯𝑯 � has many eigenfunctions and eigenvalues, and the

� is usually a differential operator, and
subscript n is used to indicate this. 𝑯𝑯
is a differential equation whose solutions give the eigenfunctions and
eigenvalues. Quantum mechanics postulates that (no matter what the state
function of the system happens to be a measurement of the property H
must yield one of the eigenvalues En of the operator 𝑯𝑯 �.

More details in the theorems………..

19
 Operators and Quantum Mechanics
we have postulated that the state of a quantum-mechanical system is
specified by a state function Ψ (q,t), which contains all the information we
can know about the system.

How does give us information about the property B? We postulate that if Ψ

� with eigenvalue bk, then a measurement of B is
(q,t) is an eigenfunction of 𝑩𝑩
certain to yield the value bk.

Consider, for example, the energy.

e − iEt / ψ ( x )
Ψ( x , t ) =
is Ψ ( x , t ) an eigenfunction of Hˆ ?
We have
ˆ − iEt / ψ ( x )
Hˆ Ψ ( x , t ) =
He
20
Operators and Quantum Mechanics

ˆ − iEt / ψ ( x )
Hˆ Ψ ( x , t ) =
He

� contains no derivatives with respect to time and therefore does not affect
𝑯𝑯
the exponential factor. We have

e − iEt /  Hˆ ψ ( x )
Hˆ Ψ ( x , t ) =
= e − iEt /  Eψ ( x )
= E Ψ( x , t )

� , and
Hence, for a stationary state, Ψ (q,t), is an eigenfunction of 𝑯𝑯
we are certain to obtain the value E when we measure the energy..

21
Schrödinger Representation

∂ momentum operator, –i times derivative with

p → Pˆ =−i 
∂ x respect to x

x → xˆ =x position operator, simply x

Operate commutator on arbitrary eigenfunction ψ.

 xˆ , Pˆ ψ = Therefore,
 
ˆ ˆ − Px
( xP ˆ ˆ )ψ =  xˆ , Pˆ ψ = i ψ
 
 ∂  ∂ and
x  −i  ψ + i  xψ
 ∂ x ∂ x  xˆ , Pˆ  = i 
 
Using the product rule
 ∂ ∂ 
= i −x ψ +ψ + x ψ
 ∂ x ∂ x 

= i ψ 22
Commutators and Simultaneous Eigenvectors

ˆ ( x) = α f ( x)
Af ˆ ( x) = β f ( x)
Bf

f ( x ) are simultaneous Eigenfunctions of operators Aˆ and Bˆ

with egenvalues α and β .

Eigenvalues of linear operators observables.

� and 𝑩𝑩
𝑨𝑨 � are different operators that represent different observables, e. g.,
energy and angular momentum.

If f(x) is a simultaneous eigenfunction of two or more linear operators

representing observables, then these observables can be
simultaneously measured.

23
 ˆ ( x) = α f ( x)
Af ˆ ( x) = β f ( x)
Bf
ˆ ˆ ( x ) = Aˆ β f ( x )
ˆ ( x ) = Bˆ α f ( x ) ABf
Bˆ Af

= α Bˆ f ( x ) = β Af
ˆ ( x)

= α β f ( x) = β α f ( x)

Therefore, Aˆ Bˆ f ( x ) = Bˆ Aˆ f ( x )
Rearranging ( Aˆ Bˆ − Bˆ Aˆ ) f ( x ) =
0

( Aˆ Bˆ − Bˆ Aˆ ) is the commutator of Aˆ and Bˆ , and since in general f ( x ) ≠ 0,

 Aˆ , Bˆ  = 0
 
The operators commute.

Operators having simultaneous eigenfunctions commute.

The eigenfunctions of commuting operators can always be constructed in such
a way that they are simultaneous e eigenfunctions.
24
Commutator Rules

[ A , B ] = − [ B , A]
A , BC ] [ A , B ] C + B [ A , C ]
[=
[=
AB , C ] [ A , C ] B + A [ B , C ]

 A , [ B , C ] +  B , [C , A] + C , [ A , B ] =

0

[ A, B + C=] [ A, B ] + [ A, C ]

25
 Integrals over operators
When we want to make contact between a calculation done using operators
and the actual outcome of an experiment, we need to evaluate certain
integrals. These integrals all have the form

=I ∫f m * Ω f n dτ
where fm* is the complex conjugate of fm. In this integral dτ is the volume
Element. If the operator is simply multiplication by 1, the integral is
called an overlap integral and commonly denoted S:

S = ∫ f m * f n dτ

It is helpful to regard S as a measure of the similarity of two functions: when

S = 0, the functions are classified as orthogonal, rather like two perpendicular
vectors. When S is close to 1, the two functions are almost identical.

26
Integrals over operators
The normalization integral is the special case for m=n. A function fm is
said to be normalized (strictly, normalized to 1) if

∫ f m * f m dτ = 1 1 = ∫ Nf m dτ
2

unnormalized
∫ f m dτ = 1 ∫
2
f m dτ
2
= N
2

.
It is almost always easy to ensure that a function is normalized by multiplying
it by an appropriate numerical factor, which is called a normalization factor,
typically denoted N and taken to be real so that N*=N.
Find the normalized form of the function f = sin(π x / l )
L
1
∫ f * fdτ ∫0= π
2 2 2
N sin ( x / L )dx LN
2
For this integral to be equal to 1, we require N = 2 / L the normalized
function is therefore 1/ 2
2
f =  sin(π x / l )
 L 27
Dirac bracket notation
In the Dirac bracket notation the integrals are written as follows

mΩn = ∫f m Ω * f m dτ m n = ∫ f m * f m dτ

Bra Ket Bra Ket

.
The combined orthonormality condition is then

m n = δ mn

And we can deduced from the definition of a Dirac bracket

m n = nm *
28
Hermitian operators
The quantum-mechanical operators that represent physical quantities are
linear. These operators must meet an additional requirement, they must be
Hermitian operators

An operator is Hermitian if it satisfies the following relation:

∫ f m* Ω f n dτ = {∫ }
f n*Ω f m dτ *

An alternative version of this definition is

∫ f m* Ω f m dτ = ∫ f ( Ωf ) *dτ
n m

This expression is obtained by taking the complex conjugate of each term on

the right-hand. In terms of the Dirac notation, the definition of hermiticity is

mΩn = nΩm *
29
About Hermitian Operators

• Property 1. The eigenvalues of hermitian operators are real.

Consider the eigenvalue equation

ω m
Ω m =

linear operator eigenvector observable value

Multiplication from the left by the bra results in the equation

m ω m=
m Ω= m ω

Now take the complex conjugate of both sides:

by hermiticity
m Ω m * ω=
= * m m * ω* mΩm =mΩm *

Therefore, it follows that ω = ω*, which implies that the eigenvalue ω is real.
30
 About Hermitian Operators
• Property 2. Eigenfunctions corresponding to different eigenvalues of an
hermitian operator are orthogonal.
Suppose we have two eigenstates that satisfy the following relations:

Ω m ω m and=
= Ω n ω´ n

Then multiplication of the first relation by n and the second by m gives

nΩ m ω nm
= =
and m Ω n ω´ m n

Now take the complex conjugate of the second relation and subtract it from
the first while using Property 1 (ω´ = ω´*):

n Ω m − m Ω n=* ω n m − ω´ m n *
0 = ( ω - ω´ ) n m
Because the two eigenvalues are different, the only way of satisfying this
relation is for 0 = n m 31
The postulates of quantum mechanics

Postulate 1. The state of a system is described by a function Ψ of the

coordinates of the particles and the time. This function, called the state
function or wave function, contains all the information that can be
determined about the system. We further postulate that Ψ is single-valued,
continuous, and quadratically integrable.

Ψ n , l , ml , m s ( q , t )

We shall see that the wavefunction of a system will be specified by a set of

labels called quantum numbers. The values of these quantum numbers
specify the wavefunction and thus allow the values of various physical
observables to be calculated.

32
The postulates of quantum mechanics

Postulate 2. To every physically observable property there corresponds a

linear Hermitian operator. To find this operator, write down the classical-
mechanical expression for the observable in terms of Cartesian coordinates
and corresponding linear momentum components, and then replace each
coordinate x by the operator x· and each momentum component px by the
operator − i  (∂ / ∂q )

• The requirement that the operators are hermitian ensures that the
observables have real values

• The requirement of linearity is closely connected to the superposition

of states

33
The postulates of quantum mechanics

Postulate 3. When a system is described by a wavefunction ψ, the mean

value of the observable Ω in a series of measurements is equal to the
expectation value of the corresponding operator.

The outcome of measurements

The expectation value of an operator Ω for an arbitrary state ψ is

denoted Ω and defined as

∫ Ω ψ dτ
ψ ψ Ωψ
*

=Ω =
∫ ψ dτ
ψ ψψ
*

If the wavefunction is chosen to be normalized to 1, then the expectation

value is simply
Ω= ∫ Ω ψ dτ= ψ Ω ψ
ψ *

34
The postulates of quantum mechanics
The meaning of Postulate 3 can be unravelled as follows. First, suppose
that ψ is an eigenfunction of Ω with eigenvalue α; then

Ω= ∫ Ω ψ dτ=
ψ ∫ ψ α ψ τ= α ∫ ψ dτ= α
ψ
* * *
d

That is, a series of experiments on identical systems to determine Ω will

give the average value ω (a real quantity, because Ω is hermitian).

Now suppose that although the system is in an eigenstate of the hamiltonian

it is not in an eigenstate of Ω.

Ω b ⇒?
normalized
In this case the wavefunction can be expressed as a linear combination of
eigenfunctions of Ω………..Superposition
35
 =
b c1 a1 + c2 a2 + c3 a3 + ⋅ ⋅ ⋅ an α n an
where Ω=

b = ∑ ci a i (If continuous range integral)

i

Consider only two states (normalized and orthogonal).

=b c1 a1 + c2 a2

Ω ( c1 a1 + c2 a2
Ω b = )
= c1Ω a1 + c2 Ω a2

= α 1c1 a1 + α 2 c2 a2
Left multiply by b .
b Ω=
b (c *
1 a1 + c2* a2 ) (α c 1 1 a1 + α 2 c2 a2 )
= α 1c1*c1 + α 2 c2*c2
= α 1 c1 + α 2 c2
2 2
36
The absolute square of the coefficient ci, | ci|2, in the expansion
of b in terms of the eigenvectors ai of the operator (observable)
Ω is the probability that a measurement of Ω on the state b
will yield the eigenvalue αi.

If there are more than two states in the expansion

b = ∑ ci a i
i

∑ α i ci
2
bΩ b =
i

eigenvalue probability of eigenvalue

37
Definition: The average is the value of a
particular outcome times its
probability, summed over all
possible outcomes.
Then

∑c αi
2
Ω= bΩ b= i
i
is the average value of the observable when many measurements are made.

Assume: One measurement on a large number

of identically prepared non - interacting systems
is the same as the average of many repeated
measurements on one such system prepared
each time in an identical manner. 38
 bΩ b ⇒ Expectation value of the operator Ω. (it is yhe
quantum mechanical average value of the observable

In terms of particular wavefunctions

∞

∫ b Ωψ bdτ
ψ ∗
bΩ b =
−∞

We can now interpret the difference between

Ω= ∫ Ω ψ dτ=
ψ ∫ ψ α ψ τ= α ∫ ψ dτ= α
ψ
* * *
d

∑c αi
2
Ω= bΩ b= i
i

Using a subsidiary postulate:

39
The postulates of quantum mechanics

Postulate 3´. When ψ is an eigenfunction of the operator Ω, the

determination of the property Ω always yields one result, namely the
corresponding eigenvalue α. The expectation value will simply be the
eigenvalue α.

When ψ is not an eigenfunction of Ω, a single measurement of the property

yields a single outcome which is one of the eigenvalues of Ω, and the
probability that a particular eigenvalue on is measured is equal to 𝑪𝑪𝒏𝒏 𝟐𝟐,
where 𝑪𝑪𝒏𝒏 is the coefficient of the eigenfunction ψ𝒏𝒏 in the expansion of the
wavefunction.

40
The postulates of quantum mechanics

Postulate 4. The probability that a particle will be found in the volume

element dτ at the point r is proportional to ψ(𝒓𝒓) 𝟐𝟐dτ

It follows from this interpretation that ψ(𝒓𝒓) 𝟐𝟐 is a probability density, in

the sense that it yields a probability when multiplied by the volume dτ of
an infinitesimal region. The wavefunction itself is a probability
amplitude, and has no direct physical meaning. Note that whereas the
probability density is real and nonnegative, the wavefunction may be
complex and negative.

It is usually convenient to use a normalized wavefunction; then the Born

interpretation becomes an equality rather than a proportionality. The
implication of the Born interpretation is that the wavefunction should be
square-integrable; that is
∫ψ dτ < ∞
2

because there must be a finite probability of finding the particle

somewhere in the whole of space 41
The postulates of quantum mechanics

Postulate 5. The time development of the state of an undisturbed quantum-

mechanical system is given by the Schrödinger time-dependent equation

∂Ψ
i  = Hˆ Ψ
∂t

� is the Hamiltonian (that is, energy) operator of the system.

where 𝑯𝑯

This partial differential equation is the celebrated Schrödinger equation

introduced by Erwin Schrödinger in 1926.

If the Hamiltonian is independent of time we can obtain the time-

dependent Schrödinger equation in one dimension (x) with a time-
independent potential energy for a single particle:

 2 d 2ψ ( x )
− 2
+ V( x )ψ ( x ) =
Eψ ( x ) 42
2m dx
The Three-Dimensional, Many-Particle Schrödinger Equation

The time-dependent Schrödinger equation for the time development of the

state function is postulated to have the form

∂Ψ
i = Hˆ Ψ
∂t
The time-independent Schrödinger equation for the energy
eigenfunctions and eigenvalues is
Ĥψ = Eψ
For a one-particle, three-dimensional system, the classical-mechanical
Hamiltonian is

1
H =T +V = ( px2 + p 2y + pz2 ) + V ( x , y , z )
2m

43
The Three-Dimensional, Many-Particle Schrödinger Equation

Introducing the quantum-mechanical operators, we have for the

Hamiltonian operator

 2
 ∂ 2
∂ 2
∂ 2

H=
ˆ −  2 + 2 + 2  + V ( x, y, z )
2 m  ∂x ∂y ∂z 
The operator in parentheses is called the Laplacian operator ∇2 (read as
“del squared”):
 ∂ 2
∂ 2
∂ 2

∇ ≡ 2 + 2 + 2
2

 ∂x ∂y ∂z 

The one-particle, three-dimensional, time-independent Schrödinger equation

is then
2 2
− ∇ ψ + Vψ =
Eψ
2m
44
 The Three-Dimensional, Many-Particle Schrödinger Equation

Now consider a three-dimensional system with n particles. The kinetic

energy is the sum of the kinetic energies of the individual particles:

1 1 1
=T ( px21 + p 2y1 + pz21 ) + ( px2 2 + p 2y 2 + pz22 ) + ..... + 2
( pxn + p 2yn + pzn
2
)
2m1 2m 2 2m n
The kinetic energy operator is
 2
 ∂ 2
∂ 2
∂ 2
  2
 ∂ 2
∂ 2
∂ 2

T=
ˆ −  2 + 2 + 2  − ...... −  2+ 2+ 2
2m1  ∂x ∂y ∂z  2 m n  ∂x ∂y ∂z 
n
 2
−∑
Tˆ = ∇ i2
i =1 2m i

 ∂ 2
∂ 2
∂ 2

∇i ≡  2 + 2 + 2 
2

 ∂x ∂y ∂z 
45
The Three-Dimensional, Many-Particle Schrödinger Equation
For a one-particle, one-dimensional system, the Born postulate states
that Ψ(𝒙𝒙, 𝒕𝒕) 2dx is the probability of observing the particle between x and x
+ dx at time t. For a three-dimensional, one-particle system, the quantity
Ψ ( x , y , z , t ) dxdydz
2

is the probability of finding the particle in the infinitesimal region of space

with its x coordinate lying between x and x + dx, its y coordinate lying
between y and y + dy, and its z coordinate between z and z + dz

46
The Three-Dimensional, Many-Particle Schrödinger Equation
Since the total probability of finding the particle is 1, the normalization
condition is
∞ ∞ ∞

∫ ∫ ∫ Ψ ( x , y , z , t ) dxdydz =
2
1
−∞ −∞ −∞

For a three-dimensional, n-particle system, we postulate that

2
Ψ ( x1 , y1 , z1 , x2 , y2 , z2 , ........ xn , yn , zn , t ) dx1dy1dz1dx2 dy2 dz2 ...dxn dyn dzn

is the probability at time t of simultaneously finding particle 1 in the

infinitesimal rectangular box-shaped region at (x1, y1, z1) with edges dx1, dy1,
dz1, particle 2 in the infinitesimal box-shaped region at (x2, y2, z2) with edges
dx2, dy2, dz2,…. and particle n in the infinitesimal box-shaped region at (xn,
yn, zn) with edges dxn, dyn, dzn.

47
 The Particle in a Three-Dimensional Box

we confine ourselves to one-particle problems. The box we consider is a

rectangular parallelepiped with edges of length a, b, and c.

0 < x < a

=
V ( x , y , z ) 0 in the region  0 < x < b
0 < x < c

V ( x , y , z ) = ∞ elsewhere

Since the probability for the particle to have infinite energy is zero, the wave
function must be zero outside the box.
48
The Particle in a Three-Dimensional Box
Within the box, the potential-energy operator is zero and the Schrödinger
equation is
 2  ∂ 2ψ ∂ 2ψ ∂ 2ψ 
−  2 + 2 + 2  + V ( x , y , z )ψ =
Eψ
2 m  ∂x ∂y ∂z 

 2  ∂ 2ψ ∂ 2ψ ∂ 2ψ 
−  2 + 2 + 2 =Eψ
2 m  ∂x ∂y ∂z 
To solve this, we assume that the solution can be written as the product of a
function of x alone times a function of y alone times a function of z alone:

ψ ( x , y , x ) = f ( x ) g(y)h( z ) separation of variables

It can be shown that, if we can find solutions of this form that satisfy the
boundary conditions, then there are no other solutions of the Schrödinger
equation that will satisfy the boundary conditions 49
The Particle in a Three-Dimensional Box
Deriving ψ
∂ 2ψ ∂ 2ψ ∂ 2ψ
′′( x ) g(y)h( z ),
f= ( x ) g′′(y)h( z ),
f= f ( x ) g (y)h′′( z )
∂x 2 ∂y 2 ∂y 2
Substitution in the Schrödinger equation
2 2 2
− f ′′ g h − f g′′ h − fgh′′ − Efgh =
0 diving by fgh
2m 2m 2m

2 2 2
− f ′′ − g′′ − h′′ − E =
0
2mf 2mg 2mh

2 2 2
− f ′′( x ) = g′′ + h′′ + E
2mf ( x ) 2mg 2mh
50
The Particle in a Three-Dimensional Box
Let define Ex as equal to the left side

2
Ex = − f ′′( x )
2mf ( x )
This definition shows that Ex is independent of y and z. Also, it shows that

2 2 2
− f ′′( x ) = E x = g′′ + h′′ + E
2m f ( x ) 2mg 2m h

independent of y, z independent of x

therefore, Ex must be independent of x. Being independent of x, y, and z, the

quantity Ex must be a constant.

51
The Particle in a Three-Dimensional Box
Similarly, we can define

2 2
Ey =
− g ′′( x ), E z =
− h′′( z )
2mg ( y ) 2mh( z )
the same reasoning that showed Ex to be a constant shows that Ey and Ez are
constants. substitution of this definitions into

2 2 2
− f ′′ − g′′ − h′′ − E =
0
2mf 2mg 2mh

gives

E x + E y + Ez =
E

52
 The Particle in a Three-Dimensional Box
We have

2 2 2
Ex =
− f ′′( x ), E y =
− g ′′( x ), E z =
− h′′( z )
2mf ( x ) 2mg ( y ) 2mh( z )

And we can rewrite these equations as:

d 2 f ( x ) 2m
+ 2 Ex f ( x) = 0
dx 2

d 2 g ( y ) 2m
+ 2 E y g( y ) =
0
dy 2

d 2 h( z ) 2m
+ 2 E z h( z ) =
0
dz 2


53
The Particle in a Three-Dimensional Box
We have converted the partial differential equation in three variables

 2  ∂ 2ψ ∂ 2ψ ∂ 2ψ 
−  2 + 2 + 2 =Eψ
2 m  ∂x ∂y ∂z 
into three ordinary differential equations

d 2 f ( x ) 2m
+ 2 Ex f ( x) = 0
dx 2

d 2 g ( y ) 2m
+ 2 E y g( y ) =
0
dy 2

d 2 h( z ) 2m
+ 2 E z h( z ) =
0
dz 2


54
 The Particle in a Three-Dimensional Box
d 2 f ( x ) 2m d 2 g ( y ) 2m d 2 h( z ) 2m
+ 2 E x f ( x ) =0, + 2 E y g( y ) =0, + 2 E z h( z ) =0
dx 2
 dy 2
 dz 2


Want to solve differential Equation, but Solution must by physically acceptable.

Born Condition on Wavefunction to make physically meaningful.

1. The wavefunction must be finite everywhere.

2. The wavefunction must be single valued
3. The wavefunction must be continuous.
4. First derivative of wavefunction must be continuous.

55
The Particle in a Three-Dimensional Box
What are the boundary conditions on

d 2 f ( x ) 2m
+ 2 Ex f ( x) =
0
dx 2

Since the wave function vanishes outside the box, continuity of ψ requires
that it vanish on the walls of the box. In particular, ψ must be zero on the
wall of the box lying in the yz plane, where x = 0, and it must be zero on
the parallel wall of the box, where x = a.

Therefore, f(0) = 0 and f(a) = 0.

56
The Particle in a Three-Dimensional Box
Comparing this equation with the Schrödinger equation for a particle in a
one-dimensional box.
d 2ψ ( x ) 2m d 2
f ( x ) 2m
+ Eψ ( x ) =
0 + 2 Ex f ( x) =
0
dx 2
 2
dx 2

particle in a one- particle in a 3D
dimensional box. dimensional box.

The equations are the same in form, Thus we can write the solution as

 nxπ x 
1/ 2
 2
f ( x) =  sin   nx 1, 2, 3....
a  a 
n x 2 h2
=Ex = 2
nx 1, 2, 3.....
8ma
57
The Particle in a Three-Dimensional Box
The same reasoning applied to the y and z equations gives

 n yπ y 
1/ 2
 2
g( y ) =  sin   n y 1, 2, 3....
b  b 
n y 2 h2
=Ey = 2
n y 1, 2, 3.....
8mb
and

 nzπ z 
1/ 2
 2
h( z ) =  sin   nz 1, 2, 3....
c  c 
nz 2 h2
=Ez = nz 1, 2, 3.....
8mc2
58
The Particle in a Three-Dimensional Box

From E x + E y + E z =
E the energy is

h nx 2
n2 2
n 2

=  2 + 2 + 2 
y z
E
8m  a b c 

As with the particle in a one-dimensional box, the ground-state energy is

greater than the classical-mechanical, lowest-energy value of zero.

Fromψ ( x , y , x ) = f ( x ) g(y)h( z ) the wave function inside the box is

 nxπ x   n yπ y   nzπ z 
1/ 2
 8 
ψ ( x, y, x ) =   sin   sin   sin  
 abc   a   b   c 

The wave function has three quantum numbers, nx, ny, nz. We can attribute
this to the three-dimensional nature of the problem. The three quantum
numbers vary independently of one another. 59
 The Particle in a Three-Dimensional Box

Since the x, y, and z factors in the wave function are each independently
normalized, the wave function is normalized:
∞ ∞ ∞ a b c

∫ ∫ ∫ ψ dxdydz ∫=
f ( x ) dx ∫ g ( y ) dy ∫ h( z ) dz 1
2 2 2 2

−∞ −∞ −∞ 0 0 0

Suppose that a = b = c. We then have a cube. The energy levels are then

=E
h2
n
8ma 2 x
2
+ n y(2
+ nz
2
)
Let us tabulate some of the allowed energies of a particle confined to a cube
with infinitely strong walls:

nxnynz 111 211 121 112 122 212 221 113 131 311
𝐸𝐸(8𝑚𝑚 𝑎𝑎2 ⁄ℎ2 ) 3 6 6 6 9 9 9 11 11 11

60
The Particle in a Three-Dimensional Box
nxnynz 111 211 121 112 122 212 221 113 131 311
𝐸𝐸(8𝑚𝑚 𝑎𝑎2 ⁄ℎ2 ) 3 6 6 6 9 9 9 11 11 11

Note that states with different quantum numbers may have the same energy

61
Energies of the lowest few states of a particle in a cubic box.
The Particle in a Three-Dimensional Box
When two or more independent wave functions correspond to states with the
same energy eigenvalue, the eigenvalue is said to be degenerate.
The degree of degeneracy (or, simply, the degeneracy) of an energy level is
the number of states that have that energy.

62
Energies of the lowest few states of a particle in a cubic box.
 Degeneracy

For an n-fold degenerate energy level, there are n independent wave

functions ψ1, ψ2,….. ψn , each having the same energy eigenvalue w:

=Hˆ ψ 1 w=
ψ 1 , Hˆ ψ 2 wψ
= 2 , .... Hψ n
ˆ wψ n

Lets prove the following important theorem: Every linear combination of

the wave functions of a degenerate level with energy eigenvalue w is an
eigenfunction of the Hamiltonian operator with eigenvalue w

linear combination
φ ≡ c1ψ 1 + c2ψ 2 + .....cnψ n
To prove this theorem, we must show that
Ĥφ = wψ 1
Hˆ (c1ψ 1 + c2ψ 2 + .....cnψ n )= w (c1ψ 1 + c2ψ 2 + .....cnψ n )
63
 Degeneracy

Acting the Hamiltonian (linear operator)

Hˆ (c1ψ 1 + c2ψ 2 + .....cnψ =

n) Hˆ (c1ψ 1 ) + Hˆ (c2ψ 2 ) + ..... Hˆ (cnψ n )
Hˆ (c1ψ 1 + c2ψ 2 + .....cnψ n )= c1 Hˆ ψ 1 + c2 Hˆ ψ 2 + .....cn Hˆ ψ n
Hˆ (c1ψ 1 + c2ψ 2 + .....cnψ n ) = c1 wψ 1 + c2 wψ 2 + .....cn wψ n
Hˆ (c ψ + c ψ + .....c ψ )= w (c ψ + c ψ + .....c ψ )
1 1 2 2 n n 1 1 2 2 n n

which completes the proof

Since any linear combination of the wave functions corresponding to a
� with the same eigenvalue,
degenerate energy level is an eigenfunction of 𝑯𝑯
we can construct an infinite number of different wave functions for any
degenerate energy level.

The degree of degeneracy of an energy level is equal to the number of linearly

independent wave functions corresponding to that value of the energy. 64