QUANTUM MECHANICS

AND ATOMIC PHYSICS

Course code; PY310
Course instructor, Ms. Andongolile, T
Department of Physics & Mathematics
 THE POSTULATES OF QUANTUM
MECHANICS
The basic questions that quantum mechanics ventures to
answer are the following:
• How can one define the state of a quantum mechanical
system at a given time t?
• How can one represent or describe a measurable physical
quantity (position, momentum, energy, angular
momentum, etc) in quantum mechanics?
• How can one calculate the values of various measurable
physical quantities in a given quantum state?
 THE POSTULATES OF QUANTUM
MECHANICS
Postulate 1
• The state of a quantum mechanical system is completely
specified by the wave function ѱ(r, t) that depends on the
particle ‘r’(x,y,z) coordinates and the time ‘t’.
Or
• Every physically realizable state of the system is described in
quantum mechanics by a state function ψ that contains all
accessible physical information about the system in that
state
• The probability that at a given instant of time, t, the
particle will be found in an infinitesimal volume
element, Δv = dxdydz, is given by
|ψ(r, t)|2dv.

• Ѱ*(r, t)Is a complex conjugate of the wave function,

obtained by replacing any imaginary numbers with
their negative:
 Properties of wave functions
i. Must be single-valued
ii. Continuous i.e. Its first (𝜕ѱ(r, 𝑡))/𝜕r and second
derivatives(first (𝜕2ѱ(r, 𝑡))/𝜕r2 must be continuous
iii. Finite
iv. The wave function is normalized i.e. ,Ѱ*(r, t)dv = 1
v. The wave function ψ(r,t) does not have any physical
meaning of its own.
vi. It should have partial derivatives
The superposition principle
• A physical system can be found in several states. For
example, a particle may be at rest or in motion, an atom
may be excited or deexcited.
• In quantum mechanics, every possible state is described by
a wavefunction ψ.
• Wavefunctions can be functions of various types of
coordinates, for example, of position ψ = ψ(r), of
momentum ψ =ψ(p), or of energy ψ = ψ(E). The choice of
the coordinates is called representation.
• Quantum systems may be in a superposition of states. i.e
if ψ1, ψ2, ..., ψk are possible states with amplitudes ck,
automatically the functions
are possible states as well.

This is called superposition principle,

• for example, a particle may be simultaneously in several
places or that an atom maybe at the same time excited and
deexcited.
Postulates 2
• To every physical observable quantity in classical mechanics
there corresponds a linear Hermitian operator in quantum
mechanics.
• An operator is a mathematical entity that acts on a
wave function to produce information about a physical
observable
• the expectation value of an operator that corresponds
to an observable must be real and therefore the
operator must be Hermitian
An operator is said to be Hermitian if it satisfies;
1) The operator  must equal its own adjoint (complex conjugate
transpose)

2) For any two functions 𝜓 and 𝜙 in the Hilbert space, the operator

⟨𝜓∣ Â 𝜙⟩=⟨ Â 𝜓∣𝜙⟩

must satisfy:

3) For any state 𝜓, the expectation value of  must be real,

⟨𝜓∣ Â ∣𝜓*⟩∈R
implies:

This aligns with the physical notion that observables (represented by

Hermitian operators) must yield real measurement results.
Some of Hermitian operator
Expectation values
Postulate 3
• In any measurement of the physical observable associated
with the operator  the only values that will ever be
observed are the eigenvalues, a, that satisfy the eigenvalue

 𝜓=a 𝜓
equation

Ψ=the eigen function of the operator Â,

a = eigenvalue
Eigenfunction
Is a special type of function that remains essentially
unchanged when a particular operator is applied to it
Eigenvalues

eigenfunction 𝜓
• A scaling factor that results when the operator  acts on

• A measurable value associated with eigenfunction

• In quantum mechanics, the momentum operator in the 𝑥-
Example

direction is given by:

function of the form ψ(x)= 𝑒(𝑖𝑘𝑥) where k is constant.

Now, consider a wave

Determine if the function is the eigenfunction of the given

operator (if so what is the eigenvalue?)
solution
When we apply the momentum operator 𝑝ˆ𝑥to 𝜓(𝑥) we get:
= -iħ(ik)𝑒𝑖𝑘𝑥 = ħk 𝑒𝑖𝑘𝑥
This simplifies to:
𝑝ˆ𝑥 ψ(𝑥) =ℏ𝑘 𝜓(𝑥)……………..1)
 𝑒𝑖𝑘𝑥= Eigen function
Where; ħk= eigenvalue

Determine if the following are eigenfunctions (if so, what are

eigen values)
Postulate 4
• If a system is in a state described by the normalized
wavefunction then the average mean value of the
observable that will be measured corresponding
corresponding to A is
• This is called the
expectation value
Postulate 5
• The wavefunction or state function of a system evolves in
time according to the time-dependent Schrodinger
• This can also be written as

The eigen value for H˄

Postulate 6
• The total wavefunction must be antisymmetric with respect
to the interchange of all coordinates of one fermion with
those of another
• Electronic spin must be included in this set of coordinates
• The Pauli exclusion principle is a direct result of this
antisymmetric
Examples
1. In quantum mechanics, a wave function 𝜓(𝑥) is
said to be allowed if it meets certain conditions.
For a particle in a one-dimensional potential,
analyze whether the following wave function is
allowed or non-allowed:
Solution
1. Consider if the 𝜓(𝑥) is finite
• For a wave to be finite must be integrable in all
i.e. |2dx = finite

Since 𝑘>0, as 𝑥→∞, 𝑒2𝑘𝑥→∞.

Therefore . |2dx diverges
between 𝑥=0 and 𝑥=𝐿. Determine whether it is allowed
Consider the following wave functions for a particle confined

based on the boundary conditions for a particle confined in a

box, and justify your answer.
1. 𝜓1(𝑥)=𝐴sin(𝑛𝜋𝑥/𝐿)
2. 𝜓2(𝑥)=𝐵𝑒𝑖𝑘𝑥
3. 𝜓3(𝑥)=𝐶(𝑥2−𝐿𝑥)
4. 𝜓4(𝑥)=𝐷cos(𝑚𝜋𝑥/𝐿)
A, B, C, and D are normalization constants, and n and m are
positive integers.
 Dirac’s notation
• It is also known as bra-ket notation,.
• Developed by Paul Dirac, this notation is essential for
representing quantum states, operators, and inner products
in Quantum mechanics
• “A physical process starting from an initial state and
reaching a final state is described by the probability

ѱ=⟨𝑓𝑖𝑛𝑎𝑙│𝑖𝑛𝑖𝑡𝑖𝑎𝑙⟩
amplitude”
Kets ∣𝜓⟩
• A ket ∣ψ⟩ represents a quantum state vector
• e.g if ∣𝜓⟩ represents the state of a particle, it could be written as
∣𝜓⟩=𝛼∣0⟩+𝛽∣1⟩,
where ∣0⟩ and ∣1⟩ are basis states and 𝛼 and β are

Bras ⟨𝜙∣
complex coefficients.

a ket ∣𝜙⟩
• Is the Hermitian conjugate (complex conjugate transpose) of

• eg, if ∣𝜙⟩=𝛼∣0⟩ + 𝛽∣1⟩ then the bra corresponding to it is

⟨ϕ∣=α∗⟨0∣ + β∗⟨1∣, where 𝛼∗and β∗ are the
complex conjugates of 𝛼 and β.
Inner Product (Bra-Ket) ⟨𝜙∣𝜓⟩
• The inner product ⟨𝜙∣𝜓⟩ represents a complex number and

∣ψ⟩ when measured in the state ∣ 𝜙⟩

gives the probability amplitude of finding the system in state

If ∣ 𝜓⟩ and ∣ 𝜙⟩ are orthonormal, then⟨𝜙∣ 𝜓⟩=0

If 𝜙≠𝜓 and ⟨𝜓∣𝜓⟩=1
Example
• E.g ΨS (n), as being the probability amplitude of observing
the particle at slit ‘n’ given that it originated from the
source S (Recall double slit experment)
• We then say that ΨS (n) is the probability amplitude of
observing the particle at the position of slit n, given that it
was originally at the position of the source S
This can be written as,
ΨS (n)=⟨n│S⟩
 Operators in Quantum Mechanics
• In quantum theory the classical mechanics parameters are
assigned certain expectation values called operators.
Operators (Â)
• Are some multiplication, differentiation rules, etc. which
act on a ѱ following them.
• Is a mathematical operation that when applied to a
function changes into another function e.g.
(Â)f(x)=g(x)
Example
• When the operator represents the differentiation w.r.t to
‘X’, the operator on a function given by
f(x)=xn
Therefore, =n.xn-1

Similarly, multiplication by ‘x’ can be considered as an

operator
x(x3+1)=(x4+x)
The function in which an operator operates is an operand
 OPERATOR ALGEBRA
The operators follow certain rules similar to those of algebra,
a few of these are given below
1. Addition and subtraction
If  and are two operators, and ‘f’ is their operand their sum is
defined as:
(Â + )f = Âf +f and (Â - )f = Âf -f

(Â + )|f⟩ = |f⟩ + |f⟩

This can be written as
Example
let = , =x then
f(x) +xf(x)= (+ x)f(x) thus operator are additive

2. Multiplication

• The meaning of Â𝐵 ̂f(x) should be that 𝐵 ̂ is first operating

• Multiplication operator are represented by

on f(x), giving a new function, and then  is operating on

that new function
Example
= , = , =-ih and f(x) =F(x)
then will be
= x( -ihf(x))
Note
• If = operators are said to be commutators
• operators are said to be anticommutators
•( = () associative property
• (Â + ) = + distributive property( imp. In fermion)
3. Commutator
The commutator of two operators and is defined as:
ѱ [Â ]= (Â − Â)ѱ
If [Â ]= 0
• The operators are said to commute, which often indicates
that they can have a common set of eigenstates.
Example:

[, 𝑖ℏ, leading to the Heisenberg uncertainty principle.

• Position and momentum do not commute, as
Example
Show if , ]f(x) commute

=-iħ(x f(x)) –(f(x) +x f(x))

= iħf(x)
Therefore, they don’t commute
Exercise
 LINEAR OPERATORS
• Are operators that operate on the sum of two functions
give the same results as the sum of two results obtained by
carrying out the same operations on the two functions
separately
• An operator is said to be linear if it satisfies the following
conditions
Â(f +g)= Âf +
Where f and g are different functions
E.gare linear operators, taking square and roots are
non-linear
LAPLACE OPERATORS
• The Laplace operator often denoted as ∇2, is a second-order
differential operator.

function 𝑓(𝑥,𝑦,𝑧) the Laplace operator is defined as:

• In three-dimensional Cartesian coordinates, for a scalar

• E.g. Schrodinger wave equation

In terms of Laplace
 HERMITIAN OPERATOR
Is an operator that satisfies the property of being equal to its

• For any two functions 𝜓 and 𝜙 in the Hilbert space, the

own complex conjugate transpose.

⟨𝜓∣ Â 𝜙⟩=⟨ Â 𝜓∣𝜙⟩

operator must satisfy to be Hermitian

The position operator acts on a wavefunction 𝜓(𝑥) as:

Example 1

𝜓(𝑥)=𝑥𝜓(𝑥)

⟨𝜙∣ 𝜓⟩
To check if is Hermitian, consider the inner product
 ⟨𝜙∣ 𝜓⟩= =

Since ⟨𝜙∣ 𝜓⟩ = ⟨ 𝜙∣𝜓⟩, is Hermitian.

= =

Example 2

𝜓(𝑥)=−𝑖ℏ
The momentum operator in the position representation is

To verify consider the inner product

⟨𝜙∣ 𝜓⟩
To verify that is Hermitian, consider the inner product
 =
Integrate by Parts

Let 𝑢=𝜙∗(𝑥)
=
v=ψ(x)
=
 = −iℏ[ϕ∗(x)ψ(x)] ​+ iℏ
[ϕ∗(x)ψ(x)] ​ =0 as x→±∞

Now consider
= iℏ………………..(a)

⟨ϕ​ ∣ψ⟩ = dx

⟨ϕ
​ ∣ψ⟩ = dx……………………….(b)

=⟨ϕ
​ ∣ψ⟩
Therefore, the momentum operator
Exercise
1. Show if the following operator are Hermitian
I. K.E operator
II. Hamiltonian operator
Parity operator( )
• The parity operator acts on a function 𝜓(𝑥) by inverting
the spatial coordinates.
• The action of the parity operator is:
ψ(x)=ψ(−x), ψ(x,y,z)=ψ(−x-y-z)

• The parity operator "flips" the sign of the spatial

coordinates.
QUANTUM MECHANICS OPERATORS
1. Position Operator ()

• Acts on the wave function 𝜓(𝑥) by simply multiplying by

• Represents the position of a particle.

𝜓(𝑥)= 𝑥𝜓(𝑥)
• Eigenstates of have definite positions

Consider a wave function in one dimension𝜓(𝑥)=𝐴𝑒𝑖𝑘𝑥 What

Example,

will be the result when an operator () acts on it?

 𝑥 ̂ 𝜓(𝑥)= 𝑥𝜓(𝑥)
The position operator in one dimension is defined by:

When the position operator acts on 𝜓(𝑥), it simply multiplies

the function by 𝑥:
𝜓(𝑥)= 𝑥⋅(𝐴𝑒𝑖𝑘𝑥)=𝐴𝑥𝑒𝑖𝑘𝑥
2. Potential energy operator
The potential energy operator in the position representation

(𝑥)=𝑉(𝑥)
is often a multiplication operator as position
3. Momentum operator
Consider a beam of electron traveling along the x-direction
can be treated as a wave propagating along the axis.
Taking these waves to be sinusoidal, the wave function may
be written as
ѱ = Asin………………………………………….(i)
An equivalent form of the time-dependent wave function is
ѱ =c𝑒
• Using the deblogie wave equation (p=h/λ)
The equation above is the form of the operator equation.
Eigen equation where Px is the linear momentum
() = Px , =ħ
() = operator for linear momentum
4. Velocity operator
The linear momentum of a particle
=.
In operator form
= m.
=
=
5.Kinetic energy operator
From momentum operator about x-axis
Pxѱ =() …………….1
Differentiate w.r.t to x,
Px = ……………………2
From eqn 1
= Pxѱ
Pxѱ. Px=
 P2xѱ=
P2xѱ = -i22
Divide this by 2m
=
Tѱ = In three-dimension Tѱ =
T=K.E=
6.Operator of total energy
Total energy of a particle moving along x-axis is the sum of
KE and PE
E = + V(x)
=
= , =V substitute this to above eqn,
= +V, =
 =
In three dimension
=
If (x,y,z) is the wave function associated with particle in a
motion, a three-dimensional time dependent Schrodinger
eqn is given as
=E