Quantum Mechanics:

Nature of Matter
Ref. H. K. Malik
 De-Broglie Hypothesis

In 1924 Louis de-Broglie proposed dual character of

matter.

“According to Louis de-Broglie, a moving matter

particle is surrounded by a wave whose wavelength
depends upon the mass of the particle and its
velocity. These waves associated with the matter
particles are known as matter waves or de-Broglie
waves”.
 de-Broglie equation provided a connection between

a wave like property of

radiation Wavelength
ℎ
𝛌=
𝑝
a particle like property Momentum

Consider a photon whose energy is given by

ℎ𝑐
𝐸 = ℎ𝑣 = … . . (1)
𝛌

where ℎ is Planck ′ s Constant = 6.62 × 10−34 𝐽 − 𝑠𝑒𝑐,

𝑣 𝑖𝑠 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦, 𝑐 𝑖𝑠 𝑡ℎ𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑔ℎ𝑡 𝑎𝑛𝑑 𝛌 𝑖𝑠 𝑡ℎ𝑒
𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑝ℎ𝑜𝑡𝑜𝑛.
If the mass of particle is converted into energy, the energy is
given by Einstein mass-energy relation as

𝐸 = 𝑚𝑐 2 … . . (2)

Equating eqns. (1) and (2), we have

ℎ𝑐
𝑚𝑐 2 =
𝛌

ℎ
𝛌=
𝑚𝑐
or where p=mc
ℎ
𝛌 = … . . (3)
𝑝
This is the wavelength of de-Broglie waves. p is the momentum
associated with photon.
❖ If in place of photon, a material particle of mass m is
moving with velocity v, then the momentum of particle
p=mv.

Therefore the wavelength of wave associated with this

moving particle is given by:

ℎ
𝛌= … . . (4)
𝑚𝑣

This wavelength is called de-Broglie wavelength. The greater

the particle momentum, the shorter its wavelength.
❖ Now we know that the kinetic energy of the material
particle of mass m moving with velocity v is given as:

2𝑣2
1 𝑚
𝐸 = 𝑚𝑣 2 =
2 2𝑚
as𝑚𝑣 = 𝑝 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚
𝑝2
𝐸=
2𝑚
or 𝑝 = 2𝑚𝐸
∴ 𝑇ℎ𝑒 𝑑𝑒 − 𝐵𝑟𝑜𝑔𝑙𝑖𝑒 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑏𝑒𝑐𝑜𝑚𝑒𝑠

ℎ ℎ
𝛌= =
𝑚𝑣 𝑝

ℎ
𝛌= … . . (5)
2𝑚𝐸
❖ According to kinetic theory of gases, the average kinetic
energy of the material particle is given by:

1 2
3
𝐸 = 𝑚𝑣 = 𝐾𝑇
2 2
whereK = 1.38 × 10 𝐽/K 𝐵𝑜𝑙𝑡𝑧𝑚𝑎𝑛𝑛′ 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
−23

T = 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒

∴ 𝐸𝑞𝑛. 5 𝑐𝑎𝑛 𝑏𝑒 𝑤𝑟𝑖𝑡𝑡𝑒𝑛 𝑎𝑠:

ℎ
𝛌= … . . (6)
3𝑚𝐾𝑇

This wavelength is called de-Broglie wavelength. The greater

the particle momentum, the shorter its wavelength.
❖ Suppose an electron accelerates through a potential
difference of V volts.
Then work done by electric field = gain in kinetic energy

1
𝑒𝑉 = 𝑚𝑣 2 … . . 7
2
where e is the electronic charge = 1.6 × 10−19 𝐶

Eqn. (7) can be written as: 𝑚2 𝑣 2 = 2𝑚𝑒𝑉

or mv = 2𝑚𝑒𝑉

∴ 𝑇ℎ𝑒 𝑑𝑒 − 𝐵𝑟𝑜𝑔𝑙𝑖𝑒 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ of the electron is given by:

ℎ
𝛌=
𝑚𝑣

ℎ
𝛌= ….. 8
2𝑚𝑒𝑉
❖ For an electron

𝑚 = 9.1 × 10−31 𝑘𝑔
e = 1.6 × 10−19 𝐶
ℎ = 6.62 × 10−34 𝐽 − 𝑠𝑒𝑐

ℎ
𝛌=
2𝑚𝑒𝑉

6.62 × 10−34 𝐽 − 𝑠𝑒𝑐

∴𝛌=
2 × 9.1 × 10−31 𝑘𝑔1.6 × 10−19 𝐶 × 𝑉

12.27
𝛌= Å….. 9
𝑉
 ℎ
𝛌=
𝑚𝑣

ℎ
𝛌=
2𝑚𝐸

ℎ
𝛌=
3𝑚𝐾𝑇

ℎ
𝛌=
2𝑚𝑒𝑉

12.27
𝛌= Å
𝑉
Properties of Matter waves

1. The de-Broglie’s wavelength of a wave associated with

moving light particle is greater than the wavelength
associated with heavier particle.

2. The de-Broglie wavelength of a wave associated with the

slow moving particle is greater than the wavelength
associated with fast moving particle.

3. For a particle at rest, that is, v=0, the de-Broglie

wavelength becomes infinite, that is, wave becomes
indeterminate and if v = ∞, 𝑡ℎ𝑒𝑛 𝛌 = 0. This indicates that
the matter waves are generated only when the material
particles are in motion.
 ℎ
4. The expression for de-Broglie wavelength (𝛌 = 𝑚𝑣 ) is
independent of charge of the particles as well as by moving
natural particles.

5. The velocity of matter wave is not constant like the

radiations which move with constant velocity equal to the
velocity of light. The velocity of matter wave depends upon
the velocity of material particle.

6. The wave and particle aspects of matter never appear

simultaneously in the same experiment.
Problems

1. What is the frequency of a photon whose energy is 66.3eV?

Ans: 1.6 X 1016Hz

2. Calculate the de-Broglie wavelength of (a) a virus particle of

mass 1.0X10-15 kg moving at a speed of 2.0 mm/sec and (b) an
electron whose kinetic energy is 120eV.
Ans: (a) 3.3X10-16 m (b) 1.1X10-10 m

3. What is de-Broglie wavelength of an electron which has

been accelerated from rest through a potential difference of
100V? Ans:1.227 Å.
4. An enclosure filled with helium is heated to 400K. A beam
of helium atom emerges out of the enclosure. Calculate de-
Broglie wavelength corresponding to He-atoms. Mass of He-
atoms is 6.7X10-27kg. Ans: 0.63 Å.
Phase Velocity
We can write the de Broglie wave travelling along the +x
direction as

where a is the amplitude, 𝜔 = 2𝜋ν is the angular frequency and k

(=2 𝜋 /λ) is the propagation constant of the wave. By the
definition, the ratio of angular frequency w to the propagation
constant k is the phase (or wave) velocity. If we represent the
phase velocity by u, then
(𝜔t - kx) is called the phase of the wave motion. It means
that the particle of the constant phase travels such that the
𝜔t-kx = constant
Thus, the wave velocity in the velocity of planes of constant
phase which advances through the medium, We can write
the phase velocity u= νλ and for an electromagnetic wave

Since c >>v, Eq. (iii) implies that the phase velocity of de

Broglie wave associated with the particle moving with
velocity v is greater than c, the velocity of light.
Group Velocity

As we have seen, the phase velocity of a wave associated with a

particle comes out to be greater than the velocity of light. This
difficulty can be overcome by assuming that each moving
particle is associated with a group of waves or a wave packet
rather than a single wave. In this context, deBroglie waves are
represented by a wave packet and hence we have group velocity
associated with them. In order to realize the concept of group
velocity, we consider the combination of two waves, resultant
of which is shown in Fig.
The two Waves are represented by the following relations
(ii)Another wave of frequency , propagation constant
and the velocity G= velocity is the velocity of envelope of
the group of waves, i.e. it is the velocity of the wave packet
(shown by dotted lines) and is known as group velocity.
Relation between Group velocity and
Particle Velocity

Consider a material particle of rest mass mo. Lets its rest mass
be m when it moves with velocity v. Then its total energy E is
given by

Its momentum is given by

The frequency of the associated deBroglie wave is given by

The frequency of the associated deBroglie wave is given by

The wavelength of the associated deBroglie wave is given by

Hence propagation constant
Since the group velocity

Thus the wave group is associated with the moving particle travels
with the same velocity as the particle. It proves that a material
particle in motion is equivalent to group of waves or a wave
packet.
 Heisenberg's Uncertainty Principle
It is impossible to determine the exact position and momentum
of a particle simultaneously.

We know that λ=h/p and k = 2π/λ

⇒ k = (2πp)/h, p = momentum of the associated particle
Consider a wave packet of matter waves of width Δx, spread in
wave number would be Δk ⇒ Δk = (2π/h) Δp

Δx ∝ 1/ Δk Δx .Δk ≅ 1 Δx.Δp ≅ h/2π

As momentum is a vector, we have then in the lowest limit of
accuracy
Δx.Δpx ≥ h/2π
Δx.Δpy ≥ h/2π
Δx.Δpz ≥ h/2π
These are Heisenberg's Uncertainty relationships
 Heisenberg's Uncertainty Principle

Uncertainty in Position : Δx

Uncertainty in Momentum: Δpx

Δx Δpx ≥ h/2π
❖ The Uncertainty Principle is an important consequence of
the wave-particle duality of matter and radiation and is
inherent to the quantum description of nature
❖ Simply stated, it is impossible to know both the exact
position and the exact momentum of an object
simultaneously
A fact of Nature!
 Heisenberg's Uncertainty Principle
- applies to all “conjugate variables”
Position & momentum: Δx . Δpx ≥ h/2π
Einstein’s photo equation: E = hf; the uncertainty in the
frequency of the matter wave is related to the uncertainty
in the energy E of the corresponding particle by
Δf = ΔE /h
Δ ω=2 π Δ f = 2 π ΔE/h;
Δ ω. Δ t ≅ 1

Energy & time: ΔE . Δt ≥ h/2π

It is not possible to determine both the energy and the time

coordinate of a particle with unlimited precision
 Some consequences of the Uncertainty Principle

❖ The path of a particle (trajectory) is not well-defined in

quantum mechanics

❖ Electrons cannot exist inside a nucleus

❖ Atomic oscillators possess a certain amount of energy known

as the zero-point energy, even at absolute zero.
The non-existence of free electron in the nucleus.
The diameter of nucleus of any atom is of the order of 10-14m. If any
electron is confined within the nucleus then the uncertainty in its
position (Δx) must not be greater than 10-14m.

According to Heisenberg’s uncertainty principle, equation

Δx Δp > h / 2π
The uncertainty in momentum is
Δp > h / 2πΔx , where Δx = 10-14m
Δp > (6.63X10-34) / (2X3.14X10-14)

i.e. Δp > 1.055X10-20 kg.m /s

This is the uncertainty in the momentum of electron and then the

momentum of the electron must be in the same order of magnitude.
The energy of the electron can be found in two ways one is by non
relativistic method and the other is by relativistic method.
Non-Relativistic method:

The kinetic energy of the electron is given by,

E = p2/ 2m

p is the momentum of the electron = 1.055X10-20 kg.m /s

m is the mass of the electron = 9.11X10-31kg
∴ E = (1.055X10-20)2/ (2X9.11X10-31) J
= 0.0610X10-9J
= 3.8X108eV

The above value for the kinetic energy indicates that an electron with a
momentum of 1.055X10-20 kg.m /s and mass of 9.11X10-31 kg to exist with
in the nucleus, it must have energy equal to or greater than this value.
But the experimental results on β decay show that the maximum kinetic
an electron can have when it is confined with in the nucleus is of the
order of 3 – 4 Mev. Therefore the free electrons cannot exist within the
nucleus
 Why isn’t the uncertainty principle apparent to us in our
ordinary experience…?
Planck’s constant, again!!

Δx . Δpx ≥ h/2π h = 6.63x10-34 [J.s]

Planck’s constant is so small that the uncertainties implied by

the principle are also too small to be observed. They are only
significant in the domain of microscopic systems.
Q.21- A nucleus in an excited state will return to its ground state,
emitting a gamma ray in the process. If its mean lifetime is 8.7
ps in a particular excited state of energy 1.32 MeV, find the
uncertainty in the energy of the corresponding emitted gamma-
ray photon.

Q.22- An atom in an excited state has a life time of 12 ns: in a

second excited state the lifetime is 23 ns. What is the uncertainty
in the energy for a photon emitted when an electron makes a
transition between these two states?

Q.23 A microscope using photons is employed to locate an

electron in an atom to within a distance of 12 pm. What is the
minimum uncertainty in the momentum of the electron located
in this way?
Q.24- Imagine playing baseball in a universe where Planck’s
constant was 0.60 J.s. What would be the uncertainty in the
position of a 0.50 kg baseball moving at 20 m/s with an
uncertainty in velocity of 1.2 m/s? Why would it be hard to catch
such a ball?

Q.25- Find the uncertainty in the location of a particle, in terms

of its de Broglie wavelength, so that the uncertainty in it velocity
is equal to its velocity.

Q.26- an electron is confined to a box the size of an atom so that

one side of the box has length d=0.1nm. (a)calculate the
uncertainty in the momentum ∆𝑝 of the electron. (b) Assuming
that the electrone is “bouncing” around inside the box with
momentum p ≈ ∆𝑝, calculate the kinetic energy of the electron.
 Wave function

Matter waves are represented by a complex function,

Ψ(x,t), which is called wave function. The wave
function is not directly associated with any physical
quantity but the square of the wave function
represents the probability density in a given region.

The wave function should satisfy the following

conditions:
(i) Ψ should be finite
(ii) Ψ should be single valued
(iii) Ψ and its first derivative should be continuous
(iv) Ψ should be normalizable.

in one dimension or

represents the position r in three dimensions.

 TIME INDEPENDENT SCHRODINGER
EQUATION
Consider a system of stationary waves associated with a
moving particle. If the position coordinates of the particle are
(x, y, z) and 𝝍 be the periodic displacement for the matter
waves at any instant of time t, then we can represent the
motion of the wave by a differential equation as follows.

where u is the velocity of wave associated with the particle. The

solution of Eq. (i) gives 𝝍 as a periodic displacement in terms
of time, i.e.
where 𝝍o is the amplitude of the particle wave at the point (x,
y, z) which is independent of time (t). It is a function of (x, y,
z). i.e., the position r and not of time t, Here.
Substituting the value of from this equation in Eq. (i),
we get
where is known as Laplacian operator. Using Eqs. (vi). (vii)
and (vii), we have

From the de Broglie wave concept

Using this relation in Eq.(ix) given

If E and V are respectively the total energy and potential
energy of the particle then its kinetic energy is given by
This is the time independent Schrodinger equation, where the
quantity 𝝍 is known as wave function. For a freely moving or
free particle V= 0. Therefore, Eq. (xii) becomes

This is called time independent Schrodinger equation for a free

particle.
 TIME DEPENDENT SCHRODINGER EQUATION

In order to obtain a time dependent Schrodinger equation, we

eliminate the total energy E from time independent Schrodinger
equation. For this we differentiate Eq. (iv) w.r.t. t and obtain

(xiv)
Substituting the value of E from Eq. (xiv) in Eq. (xii), we have

(xv)

This equation is known as Schrodinger's time dependent wave

equation.
The operator called Hamiltonian operator

and is represented by H. If we see the RHS of Eq. (xv) and keep

in mind Eq. (xiv), we notice that the operator

operating on 𝝍 gives E. Hence, Schrodinger equation can be

written in operator form, as below
OPERATORS
In a physical system, there is a quantum mechanical operator that
is associated with each measurable parameter. In quantum
mechanics, we deal with waves (wave function) rather than
discrete particles whose motion and dynamics can be described
with the deterministic equations of Newtonian physics.

Generally an operator is anything that is capable of doing

something to a function. There is an operator corresponding to
observable quantity. However, the choice of operator is arbitrary
in quantum mechanics. When an operator operates on a wave
function it must give observable quantity times the wave
function. It is a significant condition for an operator.
If we consider an operator represented by A corresponding to
the observable quantity a, then

A𝝍=a𝝍

Wave function that satisfies the above equation is called eigen

function and corresponding observable quantity is called eigen
value and the equation is called eigen value equation. Some of
those opera tabled below.
Particle in a Box (The Infinite Potential Well)

The simplest quantum mechanical problem is that of a particle

trapped in a box with infinitely hard walls. Infinitely hard walls
means the particle does not loose energy when it collides with
such walls, i.e. its total energy remains constant. A physical
example of this problem could be a molecule which is strictly
confined to a box.

Let us consider a particle restricted to move along the X-axis

between x = 0 and x = L, by ideally reflecting, infinitely high
walls of the infinite potential well, as shown in Fig. Suppose
that the potential energy Uo of the particle is zero inside the
box, but rises to infinity outside, that is,
 𝑈𝑜 > 𝐸
𝑈 𝑥 = 𝑈𝑜 → ∞;
𝑓𝑜𝑟 𝑥 ≤ 0 𝑎𝑛𝑑 𝑥 ≥ 𝐿

𝐸 > 𝑈𝑜
= 0; 𝑓𝑜𝑟 0 < 𝑥 < 𝐿

❑ A single particle of mass m confined to within a

region 0 < 𝑥 < 𝐿 with potential energy Uo = 0
bounded by infinitely high potential barriers,
i.e. Uo = ∞ for and
❑ In the regions for which the potential is infinite, the
wave function will be zero, there is zero probability
of the particle being found in these regions. Thus,
we have the boundary conditions 𝝍(0) = 𝝍(L) = 0;

❑ In the region 0 < 𝑥 < 𝐿, the potential vanishes, so

the time independent Schrodinger equation:

(i)
(ii)

(iii)
❑ The boundary conditions, have the effect of
restricting the values of the energy of the
particle. "Localization leads to quantization"
Zero-Point Energy:
The energy of
the lowest-energy
quantum state
(ground state) for
the electron bound
in an infinite well
corresponding to
n = 1 is not zero.
The wave function (or eigen function) is given by

(iii)
along with the use of expression for k.

To find the value of A, we use the normalization condition.

As mentioned earlier, the above expression simply says that the
probability of finding the particle is 1. In the present case the
particle is within the box i.e. between 0 < x < L. So the
normalization condition becomes

The normalized eigen wave function of the particle is,

therefore, given by
Q.1- An electron is conned to an infinite well whose
width L = 100 pm. (a) What are the energies of the
four least-energetic quantum states? (b) What
energy must be imparted to the electron to raise it
from a state with n = 12 to higher energy state, with
n = 25?

Ans: 6.025X10-18J = 37.6eV