Quantum Mechanics

“God does not play dice with the universe.” A. Einstein

“Not only does God play dice but... he sometimes throws
them where they cannot be seen.” Stephen Hawking

“I think I can safely say that nobody understands

quantum mechanics.” Richard Feynman
Quantum mechanics is the description of the behaviour of
matter and light in all its details. In particular, of happenings
on an atomic scale.

Atomic behaviour (like proton, neutrons, electrons, photons

etc.) is very unlike ordinary behaviour that it is very difficult
to understand and get used to it.

Classical mechanics is an approximation of quantum

mechanics.

In classical mechanics, future of the particle is completely

determined by its initial position, momentum and the forces
acting upon it.
In quantum mechanics, the initial state of the particle can
not be established with sufficient accuracy, therefore, future
of the particle has uncertainty associated with it.
 de Broglie hypothesis : A moving body behaves in a
certain way as though it has wave nature.

A photon of light of frequency ν has the momentum

hν h
p= = ; since c=ν λ
c λ
Which means wavelength of photon is specified by it
h
momentum according to λ= (1)
p

de Broglie suggested that equation (1) is completely general

and applies to material particles as well as photons.
The momentum of a particle of mass m and velocity v is
given by p = γmv, and its de Broglie wavelength will be
h
λ= (de Broglie wavelength)
γ mv
1
γ  is the relativistic factor and is given by γ=
√ 1−v /c
2 2

For non-relativistic cases, v<<c and hence γ= 1.

The greater the particle's momentum, the shorter its

wavelength.
The wave and particle aspects of moving bodies can
never be observed at the same time.

Under certain situations, a moving body resembles a wave

and in others it resembles a particle.

How the de Broglie wavelength compares with its

dimensions and the dimension of whatever it interacts with
is very important.

de Broglie had no direct experimental evidence to support

his conjecture, hence it was called hypothesis.
Proof of de Broglie hypothesis :

What if this wave source is replaced by electron gun and

then bullet gun?
 (a) (b)
The diffraction pattern of aluminium foil produced
(a) by x-rays and (b) by electrons.

“Thomson, the father, was awarded the Nobel Prize

for having shown that the electron is a particle, and
Thomson, the son, for having shown that the
electron is a wave.”
Heisenberg uncertainty principle :
“It is impossible to know both the exact position and exact
momentum of an object at the same time.”

Hence, we can not know the future because we can not

know the present.
h
Mathematically, Δ x Δ p≥
4π

If you are talking about 3 dimension then the uncertainty

principle is still true (you can not measure simultaneously
precisely position in x and px; y and py; z and pz). But you
can measure simultaneously precisely position in x and p y
(or pz) and so on.
Uncertainty principle in energy and time is given by
h
Δ E Δ t≥
4π
Planck's constant h is so small that limitation imposed by
uncertainty principle are significant only in the atomic
scale.

The uncertainties are not due to inadequate apparatus.

Doesn't matter how sophisticated an experimental set up
is, these uncertainties are fundamentally there!
why position and momentum can not be measured precisely
simultaneously
 Narrower wave group, position

can be determined more

precisely.
 Wavelength is not well defined;
not enough waves to measure λ
accurately. λ = h/γmv , hence
momentum is not precise.
● Wider wave group, position can
not be determined precisely.
● Wavelength is well defined;
enough waves to measure λ
accurately. λ = h/γmv , hence
momentum is well precise.
Significance of wave function :
The wave function is a function of x, y, z and t and is
generally a complex quantity having no direct physical
significance. The probability of finding a particle at certain
point can never be negative as probability can have values
between 0 and 1.

The wave function Ψ is not an observable quantity.

The Probability of experimentally finding the body
described by the wave function Ψ at point x,y,z, at time t is
proportional to the value of |Ψ|2 there at t.

A larger value of |Ψ|2 means stronger probability of object's

presence. A smaller value of |Ψ|2 means lesser probability
of object's presence.
Wave function Ψ = A + iB
Where A and B are real functions. The complex
conjugate Ψ* of Ψ is

Complex conjugate Ψ = A – iB

And so |Ψ|2 = Ψ* Ψ = A2 – i2B2 = A2 +B2

Hence, |Ψ|2 is a positive real quantity as required.

The linear momentum, angular momentum and energy of

the object can be established from wave function Ψ.
Normalization:
The wave function must be normalizable.
Since |Ψ|2 is the probability density of finding object
described by Ψ, integral of over all space must be finite—
because object has to be somewhere i.e.
∞

∫ dV =1
|Ψ|
−∞
2
Normalization
∞
2
If ∫
−∞
|Ψ| dV =0, the particle doesn't exist.

Obviously this integral can not be infinity and still mean

anything.
Non-normalizable wave function can not represent
particle. A normalized wave function stays normalized
for ever.
Conditions for well behaved wave function :

1. Ψ must be continuous and single valued because

probability can have one value at a particular place and
time, and continuous.

2. Momentum considerations require that partial

derivatives ∂Ψ/∂x, ∂Ψ/∂y and ∂Ψ/∂z be finite, continuous,
and single valued.

3. Ψ must be normalizable which means that Ψ must go

to zero as x→±∞, y→±∞, z→±∞ in order that probability
of finding the object over all space is finite constant.
For a normalizable wave function, the probability that
the particle will be found between x 1 and x2 (if motion is
restricted in x direction) is given by

x2

P x x =∫|Ψ|2 dx
1 2
x1
Expectation value : how to extract information from a
wave function.

The wave function Ψ(x,y,z,t) contains all information about

the particle permitted by uncertainty principle.

Suppose if a particle is confined in x-direction, then

expectation value <x> of position of the particle described
by wave function Ψ(x,y,z,t) can be calculated.
Average position x of number of identical particles
distributed along x-axis such that N1 particles are at x1, N2
are at x2, N3 are at x3 and so on is given by
N 1 x 1 + N 2 x 2 + N 3 x 3 +...... ∑ N i x i
x= = (2)
N 1 + N 2 + N 3 +...... ∑ Ni
When dealing with single particle, the number N i of particles
at xi is replaced by the probability Pi that the particle is
found in interval dx at xi. This probability is :
2
Pi =|Ψ |dxi

Where Ψi is the particle wave function at x i. Making these

substitutions in equation (2), the expectation value of the
position of a single particle is given by
∞

∫ x|Ψ| dx
2
(3)
⟨ x ⟩= −∞
∞

∫
−∞
|Ψ| dx
2
 ∞

∫ x|Ψ| dx2

⟨ x ⟩= −∞
∞ (3)
∫
−∞
2
|Ψ| dx

If Ψ is a normalized wave function then denominator in

Eq. (3) is 1 (because the particle exists somewhere
between x = +∞ and x = -∞). In that case
∞
⟨ x ⟩= ∫ x|Ψ| dx
Expectation value 2

for position −∞

Physically <x> is the average of measurements performed

on particles all in the state Ψ.
It doesn’t mean that if you measure position of one particle
Again and again, <x> will be the average of the results.
Expectation value <G(x)> of any quantity that is function
of x for example potential energy can be calculated in this
way
∞
2
Expectation value ⟨G( x)⟩= ∫ G ( x)|Ψ| dx
−∞
The expectation value of momentum can not be
calculated this way because uncertainty principle doesn't
allow that because p(x) = mv = m (dx/dt);

If x is specified then Δx = 0 and then corresponding

momentum p can not be specified because Δx Δp ≥ h/4π.

The same problem occurs for the expectation value of

energy <E> as well. The expectation values <p> and <E>
are calculated in other way (operators are used).

Again, this kind of limitation is not observed in classical

mechanics.
Operators (another way to calculate expectation value) :
A free particle wave function is given by Ψ= A e−(i / ℏ)(Et− px)
Differentiating above equation w.r.t. x and t gives

∂ Ψ = i p A e−(i/ ℏ )( Et− px )= i p Ψ
∂x ℏ ℏ
ℏ ∂
⇒ p Ψ= Ψ
i ∂x
∂ Ψ i −(i/ ℏ )(Et− px ) i
similarly =− E A e =− E Ψ
∂t ℏ ℏ
⇒ E Ψ=i ℏ ∂ Ψ
∂t
 ℏ ∂ ∂
p Ψ= Ψ ⇒ p =−i ℏ
^
i ∂x ∂x
E Ψ=i ℏ ∂ ^
Ψ ⇒ E=i ℏ ∂
∂t ∂t
An operator tells us what operation to carry on quantity
following it. E and p are operators.
Even if they are derived for free particle, they are entirely
general. In that case, E is sum of K.E. and P.E.
2
p
E= +U
2m
multiplying both sides by Ψ
2
p
⇒ E Ψ= Ψ +U Ψ
2m
2
ℏ 2
i ℏ ∂ Ψ =− ( ∂ Ψ2 )+ U Ψ Schrodinger equation
∂t 2m ∂ x in 1-d
Expectation value of p for normalized wave function is
given by ∞ ∞
⟨ p⟩= ∫ Ψ p^ Ψ dx= ∫ Ψ (−i ℏ ∂ ) Ψ dx
* *

−∞ −∞ ∂x
∞
*∂Ψ
=−i ℏ ∫ Ψ dx
−∞ ∂x
Expectation value of E is given by
∞ ∞
* * ∂
⟨ E ⟩= ∫ Ψ E Ψ dx= ∫ Ψ (i ℏ ) Ψ dx
^
−∞ −∞ ∂t
∞
=i ℏ ∫ Ψ * ∂ Ψ dx
−∞ ∂t
Remember operators have to be in between Ψ* and Ψ.
Expectation value of observable G(x,p) can be calculated as
∞
⟨G( x , p)⟩= ∫ Ψ G
*
^ Ψ dx
−∞
Schrodinger Equation :
A basic principle (like Newton’s law in classical
mechanics) that can not be derived from anything else.
2
ℏ 2 2 2
i ℏ ∂ Ψ =− ( ∂ Ψ2 + ∂ Ψ2 + ∂ Ψ2 )+U Ψ
∂t 2m ∂x ∂y ∂z
Where m is mass of the particle and U is the potential
energy of the particle.

If the particle motion is limited to 1-dimension (x,t) the

above equation becomes
2
∂ Ψ ℏ ∂ 2
Ψ
iℏ =− ( )+U Ψ
∂t 2m ∂ x 2
Time-independent Schrodinger equation :
For a particle whose potential energy doesn’t depend on
time explicitly, forces acting on the particle and hence,
potential energy U, vary with position of the particle only. In
that case, Schrodinger equation can be simplified by
removing reference to t.
The wave function can be written as Ψ ( x , t )=ϕ( x) f (t )
∂ Ψ ( x , t ) d ϕ( x)
= f (t )
∂x dx
2 2
∂ Ψ ( x , t ) d ϕ( x)
2
= 2
f (t ) (4)
∂x dx
∂ Ψ(x ,t) df (t ) (5)
=ϕ( x)
∂t dt
Using equation (4) and (5) in Schrodinger equation
2
ℏ 2
i ℏ ∂ Ψ =− ( ∂ Ψ2 )+U Ψ gives
∂t 2m ∂ x
2 2
df (t) ℏ d ϕ( x)
i ℏ ϕ( x) =− f (t) 2
+U ϕ( x) f (t )
dt 2m dx
Dividing both sides by ϕ( x) f (t )
2 2
1 df (t ) ℏ 1 d ϕ( x)
iℏ =− 2
+U
f (t ) dt 2 m ϕ( x) dx
L.H.S. is function of t only and the R.H.S. is function of x
only. This can only be possible if both sides are
constant--Otherwise by varying t, we can change L.H.S.
without touching R.H.S. and two will no longer be equal.
 The constant is energy E. Then
(I am getting rid of writing f
1 df as function of t and Ф as
iℏ =E
f dt function of x).
df iE
⇒ =− f (6)
dt ℏ
2
ℏ d2 ϕ
and ,− +U ϕ=E ϕ (7)
2 m dx 2

Equation (7) is called time-independent (steady state)

Schrodinger equation. General solution for equation (6) is
given by −iEt
ℏ
f (t )=C e
−iEt Constant C is
Hence , Ψ ( x , t )=ϕ( x)e ℏ absorbed in Ф(x).
 2
ℏ d2 ϕ
− +U ϕ=E ϕ (7)
2
2 m dx

In three dimesions, equation (7) can be written as

2
ℏ d2 ϕ d2 ϕ d2 ϕ
− ( 2 + 2 + 2 )+U ϕ=E ϕ
2 m dx dy dz
Eigenvalues and Eigenfunctions :

The values of energy En for which Schrodinger's steady-

state equation can be solved are called eigenvalues and
the corresponding wave functions Φn are called
eigenfunctions.
The condition that the variable G be quantized is that the
following condition should be satisfied:

Eigenvalue equation : ^ ϕn=G n ϕn

G
Each Gn is a real number.
If measurements of G are made on a number of identical
systems all in states described by the particular
eigenfunction Φn, each measurement will yield the single
value Gn.
 Schrodinger equation in 1-d is given by
2
ℏ d2 ϕ (7)
− +U ϕ=E ϕ
2 m dx 2

2 2
^ =− ℏ d Hamiltonian operator
⇒H +U
2 m dx 2
in such steady-state Schrodinger equation
^ ϕ n=E n ϕn
H

This leads to quantization of energy.

Particle in a box or infinite well : particle in a box
with infinitely hard walls (particle doesn't lose energy each
time it strikes a wall).
Consider a particle of mass m trapped in a box of length L,
the particle motion is restricted to x = 0 to x = L. For
convenience, the potential energy U is taken to be zero
inside the box and infinite for x < 0 and x > L.

Since particle can not have infinite

energy, it can not exist outside
box, and so the wave function Φ
is zero for x ≤ 0 and x ≥ L.
The Schrodinger equation is given by
2
ℏ d2 ϕ
− +U ϕ=E ϕ
2 m dx 2

For particle inside the box, above equation becomes

2
d ϕ 2 mE (Remember U=0
2
+ 2 ϕ=0 inside box)
dx ℏ
The general solution of this equation (S.H.O.) is given by

ϕ= A sin √ 2 mE
x+B cos √ 2 mE
x (8)
ℏ ℏ
The solution given by (8) is subjected to boundary
condition: wave function must vanish for x=0 and x=L (i.e.
Φ=0 for x=0 and x=L). A and B are constants to be
calculated.
 ϕ= A sin √ 2 mE
x+B cos √ 2 mE
x (8)
ℏ ℏ
At x=0, cos (0) =1, therefore second term in equation (8)
can not describe the particle because it does not vanish at
x=0 (remember well behaved wave function must be
continuous). Therefore, B=0.

ϕ= A sin √ 2 mE
x (9)
ℏ
At x=0, sin(0)=0. Hence Φ=0 at x=0. But Φ must also
vanish at x=L which is possible if

√ 2 mE L=n π n = 1,2,3……….. (10)

ℏ
 √ 2 mE L=n π n = 1,2,3……….. (10)
ℏ
From equation (10) it is clear that energy of the particle
can have certain values, which are eigenvalues. These
eigenvalues constitute energy levels of the system and are
given by (10) as

2 2 2
nπℏ n π ℏ
√(2 mE n )= L ⇒ 2 mEn= 2
L
n2 π 2 ℏ 2
E n= n=1,2,3 …… (11)
2 mL2
 2 2 2
n π ℏ n=1,2,3 …… (11)
E n= 2
2 mL
Each permitted energy is called an energy level and the
integer n specifying an energy level En is called its
quantum number.
Conclusions :
1. Trapped particle can not have an arbitrary energy.
Boundary conditions or its confinement restricts its
wave function and hence particle is allowed to have
only certain specific energies and no others (No
counterpart in classical). Exact energies depend on
mass of particle and details how it is trapped.
2.Because Planck's constant is so small – quantization
of energy clearly noticeable only when m and L are
also small.
3. A trapped particle can not have zero energy. The de
Broglie wavelength (λ = h/mv) is infinite when v=0. There
is no way a trapped particle can have an infinite
wavelength, so particle must have at least some kinetic
energy. Exclusion of E=0 has no counterpart in classical
physics.

4. Energy levels are not equally spaced. En  n2

2 2 2
n π ℏ n=1,2,3 …… (11)
E n= 2
2 mL
Wavefunction :
The wavefunction of particle in a box whose energy
is En is given by
2 2 2
ϕ = A sin
√ 2 mE n
x Putting E n=
n π ℏ
n 2
ℏ 2 mL
We get

√
2 2 2
n π ℏ nπℏ
2m 2
2 mL L nπ x
ϕ n= A sin x= A sin x= A sin
ℏ ℏ L
n=1,2,3 ……
 nπ x
ϕ n= A sin n=1,2,3 ……
L
Φn is a well behave wave function because :
1. For each value of n, Φn is finite, single valued function
of x and Φn and ∂Φn/∂x are continuous.
2. The integral |Φn|2 over all space is finite.
∞ L L
2 2 2 nπ x 2
∫
−∞
|ϕ n| dx=∫|ϕ n| dx= A ∫ sin (
L
) dx
0 0
2 L
A 2nπ x
=
2
∫ (1−cos( L ))dx
0
2 L L
A 2nπ x
= [∫ dx−∫ cos( )dx ]
2 0 0 L
 2 L L
A 2nπ x
= [∫ dx−∫ cos( ) dx ]
2 0 0 L
2 L
A L 2n π x
= [ x− sin ( )]
2 2nπ L 0
2
A L 2n π L L 2nπ 0
= [ L− sin( )−0− sin( )]
2 2nπ L 2nπ L
2 L
=A ( )
2
∞
2 L
i.e. 2
⇒ ∫ |ϕn| dx= A ( ) (12)
−∞ 2
But if Φ is to be normalized that means A should be
assigned a value such that equation (12) should be equal to
1.
 ∞
L (because Φn has to be
⇒ ∫ |ϕ n| dx= A ( )=1
2 2

−∞ 2 normalized)

⇒ A=
2
L√
Therefore the normalized wave function Φn is given by

ϕn=
2
L
sin
√nπ x
L
n = 1,2,3………...

ϕ1 =
√2
L
sin
πx
L
; ϕ2=
√2
L
sin
2π x
L
ϕ3=
2
L √
sin
3πx
L
 The ground state (lowest energy) of this particle :
when x = 0, Φ1 = 0
ϕ1 =
2
L √
sin
πx
L
; when x = L/2, Φ1 = max
when x = L, Φ1=0

Φ1 |Φ1|2

0 L x
0 L x

Particle has the maximum probability to be in the middle

of box in the lowest energy state.
 when x = 0, Φ2 = 0
when x = L/4, Φ2 = max
ϕ 2=
√2
L
sin
2π x
L
when x = L/2, Φ2 = 0
when x = 3L/4, Φ2 = min (-ve)
when x = L, Φ2= 0

Φ2 |Φ2|2

0 L/2 L x 0 L/2 L

Particle has the minimum probability to be in the middle of

box in the first excited energy state.
 ϕ3 =
2
L √
sin
3πx
L
(work it out yourself)

Φ3 |Φ3|2

0 L/2 L x 0 L/2 L
 Comparison of different states :

Φ3 |Φ3|2

Φ2 |Φ2|2

Φ1 |Φ1|2
x=
x=0 x=L x=0 x=0
0
Classical physics, of course, suggests same probability
for the particle being anywhere in the box.
Tunneling : Another phenomenon that can be explained
only quantum mechanically. No classical counter part.

Potential energies are never infinite in real world and well

with infinitely hard walls (infinite potential well) has no
physical counterpart.

In real world, we deal with potential barriers of finite

height.
 U
E<U
E
Energy

  
x=0 x=L x

Φ+ Φ+
Φ
Φ-
x=0 x=L x

On both sides of barrier U=0, no forces act on the particle

there. Barrier height is “U” and width is “L”.
Φ+ : Incoming beam of particles moving to the right.
Φ- : Reflected particles moving to the left.
Φ : Particles inside the barrier, some of which end up in
region while others return to .
Φ : Transmitted particles moving to the right.

The transmission probability for a particle to pass

through The barrier is equal to fraction of incident beam
that gets through the barrier.
Transmission probability is given by T =e−2 k 2 L where

k2 =
√ 2 m(U −E) m is mass of the particle, E is K.E.
ℏ and U is barrier height, L is width
of the barrier.
Classical Mechanically, when energy of the particle is
less than barrier height U, particle must be reflected
back. In QM, the de Broglie waves corresponding to
particle are partly reflected and partly transmitted.

If the barrier is infinitely thick then the transmission

probability will be zero. But if it is of finite thickness there
is finite probability-however small- for particle to tunnel
through region  and emerge in region .

Particle doesn't go over the top of the barrier, but tunnels

through the barrier.

The higher the barrier and wider it is, less will be the
chance that the particle can get through the barrier.