QUANTUM MECHANICS

INTRODUCTION

 Classical Physics could not properly explain many physical

phenomena observed in the atomic and subatomic
domain. Max Planck in 1900 put forward the quantum
theory to explain the black body radiation. In 1905, Einstein
introduced the idea of light quantum or photon in
explaining photoelectric effect. The particle nature of
radiation was stressed in these theories. But wave nature
of radiation was essential for the explanation of
interference, diffraction and polarization. In 1912, Neils
Bohr proposed the theory of hydrogen spectrum. He
incorporated both classical and quantum concepts into his
theory
 DE BROGLIE WAVES ( MATTER
WAVES)

 In 1924, Louis de Broglie of France proposed that just

like radiation, particles also have a dual nature. They
behave like particles and waves.

 Waves associated with particle in motion are called
matter waves or de Broglie waves.
 Consider a photon of light of frequency υ. Its Energy,
E = h υ ….(1), where h is the Planck’s constant.
 But from relativistic concept, E= 𝑝2𝑐2 + 𝑚02𝑐4 ,
 But for photon 𝑚0=0, So E= pc….(2)
 From (1) and (2), h υ= pc or p= h/ λ , since c= υ λ

 Therefore, the photon wavelength, λ=h/p ,de Broglie
suggested that the equation is a completely general
one that applies to material particles like electrons,
protons, atoms, molecules etc. as well as to photons.
The momentum of a particle of mass m and velocity v
is p = mv and
 its de Broglie wavelength is given by λ=h/mv .
 Wavelength of an electron
 The wavelength of an electron is  = h/mv
 An electron accelerated from rest through a potential
difference gives 12mv2 =eV or v= 2𝑒𝑉
𝑚

 Therefore λ=h/mv = ℎ
2𝑚𝑒𝑉
Substituting the values of
constants we get

 λ= 150
𝑉
A0
 Properties of matter waves

1. It exhibit dffraction phenomena( Davisson and

Germer Expt)
2. Neither electromagnetic nor acoustic waves
3. Does not require any material medium.
 WAVE FUNCTION

 A moving particle (like a moving electron) can be

considered as a wave group or a packet of waves.
 In a wave, there is something that varies periodically
 The quantity whose variations make up matter waves is
called the wave function and it is denoted by the Greek
letter 𝛹.
 𝛹 is a mathematical function which describes the state of
a particle or a system.
 It is a function of position co-ordinates and time.
 It is, in general, a complex function
Probability interpretation of wave
function.

 𝛹* 𝛹 or │ 𝛹 │2 represents the probability density or the

probability of finding the particle in unit volume. If a
particle exists in a given region of space, the total
probability of finding the particle in that region is one.
 In mathematical form as ‫𝑑 𝛹 ∗𝛹 ׬‬τ = 1…….(1)
 where 𝑑τ is the volume element. Equation (1) is called the
normalisation condition.
 𝛹 is not an observable. But 𝛹* 𝛹 is an observable. This is
the statistical interpretation (Copenhagen interpretation)
of 𝛹 .
THE SCHRODINGER EQUATION
 The differential equation for a wave associated with a
particle and propagating along the X-direction may be
𝜕2𝛹 𝜕2𝛹
 written as 𝜕𝑥2 1
=
𝑣
2 .
𝜕𝑡2
 A solution to this equation is 𝛹=ae i(kx-ωt)
 where k= 2π/λ and ω=2π/T, a is the amplitude of the wave;
T, the period and λ the wavelength.
 If υ is the frequency of the wave, ω=2π/T= 2πυ =E/ħ where
E is the energy of the particle and ħ=h/ 2π
 k= 2π/λ= 2πp/h= p/ħ
 Hence, the wave function for a particleof energy E and
𝑖
ħ(px-Et) ……….(1)
momentum p may be written as 𝛹=ae
THE SCHRODINGER EQUATION
𝜕ψ
 Differentiating equation (1) w.r. to t, = -ħ𝑖 Eψ
𝜕𝑡
𝜕ψ
 On arranging we get E ψ= iħ ……..(2)
𝜕𝑡
𝜕ψ 𝑖
 Differentiating equation (1) w.r. to x twice , = 𝑝ψ
𝜕𝑥 ħ
𝜕2ψ 𝑝2 𝜕2ψ
 = - ħ2
ψ or p2ψ= -ħ2 ……….(3)
𝜕𝑥2 𝜕𝑥2
 The total energy E of the particle is the sum of the kinetic and
potential energies
𝑝2
 E= 2𝑚 +V
𝑝2
 Multiplying by ψ, E ψ = 2𝑚 ψ + V ψ …………(4)
 Substituting equation (2) & (3) in (4)
2
𝜕ψ ħ2 𝜕 ψ
 iħ = -2𝑚 2 + V ψ …………………(5)
𝜕𝑡 𝜕𝑥
This is the one-dimensional time-dependent Schrodinger equation.
 THE SCHRODINGER EQUATION
 In a number of cases, potential energy V of a particle does not depend on
time; it varies with the position of the particle only and the field is said to
be stationary. In such stationary problems, Schrodinger equation can be
simplified by separating out time-dependent and positiondependent
parts. Accordingly, we can write the wave function ψ(x,t) as a product of
a function of position x; f(x) and a function of time Φ(t).
ie:- ψ(x,t) = f(x) Φ(t) ……..(6)
𝜕2ψ 𝜕2𝑓
Differentiating (6) with respect to ‘x’ twice, 2 = Φ 2 ..(7)
𝜕𝑥 𝜕𝑥
𝜕ψ 𝜕Φ
Differentiating (6) w. r. to ‘t’, =f ……..(8)
𝜕𝑡 𝜕𝑡
Substituting (7) and (8) in (5)
𝜕Φ 2 𝜕2𝑓
iħ f 𝜕𝑡 = -2𝑚 Φ𝜕𝑥2 + V f Φ
ħ

Dividing throughout by f Φ
1 𝜕Φ
2𝑓
ħ 1 𝜕
2
iħ Φ = -2𝑚 𝑓 2 + V ………(9)
𝜕𝑡 𝜕𝑥
 THE SCHRODINGER EQUATION
 The LHS of eqn.(9) is a function of t alone while the RHS is a function of
x alone. For the equation to be consistent, each side must be equal to
𝜕Φ
same constant, K .Equating the LHS of (9) with K, we get iħ Φ1 𝜕𝑡 =K
𝜕Φ −𝑖 dΦ
= K 𝜕𝑡 or = −𝑖 K d𝑡
Φ ħ Φ
𝑖
ħ
Integrating Φ = 𝑒 −ħ 𝐾𝑡
𝑖
− 𝐾𝑡
Equation (6) becomes ψ(x,t) = f(x) 𝑒 ħ ……(10)
𝜕ψ −𝑖
Differentiating (10) [Link] t = Kψ
𝜕𝑡 ħ
𝜕ψ
iħ 𝜕𝑡 = K ψ………….(11)
 Comparing (11) with (2), we find that K is identical with E, the total
energy. Equating the RHS of eqn. (9) to E, we get
2 𝜕2𝑓 𝜕2𝑓 2𝑚
 -ħ 1
+ V =E or 𝜕𝑥2 + ħ2 (E-V) f =0 or put f(x)= ψ(x)
2𝑚 𝑓𝜕𝑥2
𝜕2ψ 2𝑚
 We get 𝜕𝑥2
+ ħ2 (E-V) ψ=0 .
 This is Schrodinger’s time- independent equation in one dimension
 It is also called the steady state form of Schrodinger’s equation
Characteristics of a wave function
 For studying the nature of moving particles,we have to
find the potential energy V of the particle. This is to be
substituted in the Schrodinger equation and the equation
should be solved to find ψ. It will give valuable
information regarding the properties of the particles. The
wave functions obtained as solutions to the Schrodinger
equation must be well-behaved. i.e., ψ should be
1. finite, and should tend to zero when x tends to infinity .
2. ψ(x) should be single -valued at a point and
𝜕ψ 𝜕2ψ
3. ψ(x) , , 2 etc. should be continuous.
𝜕𝑥 𝜕𝑥
 APPLICATIONS OF QUANTUM
MECHANICS- PARTICLE IN A ONE
DIMENSIONAL BOX
 Consider a particle of mass ‘m’
 confined in a one dimensional
potential box, of infinite depth
and finite width L, moving in the
X direction. In order to ensure
that the particle remains in the
box , we shall assume that V = 0
every where within the box and V
= infinity outside the box.
PARTICLE IN A ONE DIMENSIONAL
BOX

 The Schrodinger equation for this single particle is

𝜕2ψ
 + 2𝑚
ħ2
Eψ=0 …….(1)
𝜕𝑥2

𝜕2ψ
ie:- + k2ψ=0 …….(2) where k2 = 2𝑚
ħ2
E…….(2a)
𝜕𝑥2
The general solution to this equation can be written as

 ψ= 𝐴𝑒 𝑖𝑘𝑥 + B𝑒 −𝑖𝑘𝑥 …….(3) where A and B are constants

 to be determined using appropriate boundary conditions.
 The probability of finding the particle outside the box is
zero. ie:- ψ* ψ= 0 outside the box.
 If the wave function is to be continuous, ψ* ψ must be
zero at the walls of the box and outside.

 This means ψ itself must be zero at the walls. Left side

boundary condition is Ψ= 0 when x = 0
PARTICLE INA ONE DIMENSIONAL
BOX
 Apply this to eqn. (3).

 Thus, 0 = A + B

 or B = – A

 Equation (3) then becomes ψ = 𝐴𝑒 𝑖𝑘𝑥 -A 𝑒 −𝑖𝑘𝑥


 ψ =2iAsin kx

 or ψ =C sin kx ……..(4) where C = 2i A

 Equation (4) obeys both the Schrodinger equation

and the first boundary condition.
 Right side boundary condition is ψ=0 when x = L

 Apply this to equ. (4)


 0= Csin kL ……(5)

 Since C ≠0,

 sin kL = 0 or kL = nπ where n = 0, 1, 2, 3, ......

 or k= 𝑛π
𝐿
…………..(6)
 PARTICLE INA ONE DIMENSIONAL
BOX
 Substituting eqn (6) in (4)

𝑛πx
 we get ψ =C sin ……..(7)
𝐿

 Equation (7) is a satisfactory solution obeying the boundary

conditions. We shall now evaluate C by applying the
normalisation condition.
 𝐿 𝑛πx
 ‫ׯ‬0 (C sin ) 2 dx =1
𝐿

 On solving we get C= 2
𝐿

𝑛πx
Substituting for C in equation (7) ψ = 2
𝐿
sin 𝐿 …..(8)

where n = 0, 1, 2, 3, ....
 If n = 0, ψ =0 &

 𝛹* 𝛹 =0, every where inside the box, which is notpossible.

 Hence zero should be discarded from the possible values

 of n. The new possible values of n are n = 1, 2, 3, 4, ........

 As n changes, there is an infinite number of satisfactory discrete

functions, each involving a different integral value of n. (n is called
a quantum number)
 ALLOWED ENERGY LEVELS
 From eqn (6) k= 𝑛π
𝐿

 Also from eqn (2a), k2 = 2𝑚
ħ2
E

2𝑚 𝑛2 2
π
There fore, ħ2
E = 𝐿2

Possible energy of electrons in the nth level is

2 2 2
𝑛π ħ
En = 2𝑚𝐿2
……(9) where n = 1, 2, 3....
Equation (9) expresses the stationary energy states possible to
the particle in the [Link] state of the particle characterised by
any particular value of the allowed energy levels is called a
quantum state.

 n = 1 corresponds to the first quantum state. The first quantum

state is also called the ground state. The energy of a particle in a
box in the ground state is obtained from equation (9) by
putting n = 1.
 π2ħ2
 E1 = and
2𝑚𝐿2

4π2ħ2
 E2 = 2𝑚𝐿2
for n=2 and so on
ALLOWED ENERGY LEVELS
 The wave functions and probability densities for a single particle
in a one dimensional box are

𝑛πx
ψ = 2
𝐿
sin and
𝐿

𝑛πx
|ψ |2 = 2
𝐿
sin2 where n = 1, 2, 3, ....
𝐿
 QUANTUM MECHANICAL
TUNNELLING

 According to classical mechanics, when a particle of kinetic

energy E approaches a potential barrier V, (E < V) it bounces
off without entering the otherside. But in quantum
mechanics the wave function representing the particle wave
does not vanish on the other side of the barrier. This shows, a
finite probability of the particle penetrating the barrier. The
phenomenon of penetration of particles through barriers
higher than their own incident energy is known as tunnelling.
 Consider a beam of identical particles of kinetic
energy E. Let the beam be incident from the left on a
potential barrier of height V and width L. On either
side of the barrier, V = 0, which means that no forces
act on the particles there. The potential can be
represented as V = 0 for x < 0 (region I), V = V for 0 < x
< L (region II) and V= 0 for x > L (region III). Let ψ1 ,
ψ2 and ψ3 be the wave functions in regions I, II and III
respectively.
 QUANTUM MECHANICAL
TUNNELLING

 The Schrodinger
2
equation for the particles in these regions
𝜕ψ
are 𝜕𝑥21 + 2𝑚
ħ2
Eψ1=0 ………(1)
𝜕2ψ2 2𝑚 𝜕2ψ3 2𝑚
 𝜕𝑥2
+ ħ2 (E-V)ψ2=0…….(2) and 𝜕𝑥2 + ħ2 Eψ3=0……(3)
 According to classical mechanics, when a particle of kinetic
energy E < V approaches a potential barrier, the particle
must be reflected. In quantum mechanics, the de Broglie
waves that correspond to the particle are partly reflected
and partly transmitted. This means that the particle has a
finite chance to penetrate the barrier.
 The solutions to equations (1) and (3) are
ψ1=𝐴𝑒 𝑖𝑘1𝑥 +B
𝑒 −𝑖𝑘1𝑥 … . . 4 and ψ3=𝐸𝑒 𝑖𝑘1𝑥 +𝐹𝑒 −𝑖𝑘1𝑥 … . 5 where k1
= 2𝑚𝐸
ħ
is the wave number of the de Broglie waves that
represent the particles outside the barrier.
 QUANTUM MECHANICAL
TUNNELLING

 The term Aeik1x in equation (4) represents a wave of

amplitude A incident from the left on the barrier. This
wave strikes the barrier at x = 0 and is partly
transmitted and partly [Link] term Be-ik1x in
equation (4) represents the reflected wave. On the
far side of the barrier (x > L) there can only be a wave
represented by Eeik1x , the transmitted wave travelling
in the +X direction since region III contains nothing
that could reflect the wave. Hence F = 0 and
ψ3=𝐸𝑒 𝑖𝑘1𝑥
 QUANTUM MECHANICAL
TUNNELLING
𝜕2ψ2 2𝑚
 Equation (2) can be written as - (V-E)ψ2=0...(7)
𝜕𝑥2 ħ2
 Solution of equ. (7) can be written asψ2=𝐶𝑒 𝑘2𝑥 −𝑘2𝑥
+𝐷𝑒 .(8)
 where k2 = 2𝑚(𝑉−𝐸)
ħ
is the wave number of the de Broglie
waves that represent the particles inside the barrier.
 As the exponents in equation (8) are real, ψ2 does not
oscillate and therefore does not represent a moving
particle. However the probability density | ψ2 |2 is not zero.
Hence there is a finite probability of finding the particle
within the barrier. Such a particle may emerge into region
III.
 Transmission probability ( T ) for a particle to pass
through the barrier is defined as the ratio of the flux
of particles (number of particles per unit area per
second) that emerges from the barrier to the flux of
particles that arrives at it.
 T=EE*/AA*
 T α e-2k2L
 QUANTUM MECHANICAL
TUNNELLING

 Tunnel effect occurs in the case of α-particles emitted

by certain radioactive nuclei. It is found that an α -
particle whose kinetic energy is only a few MeV is able
to escape from a nucleus whose potential wall is of
height 25 MeV. This effect is made use of in the
operation of tunnel diodes and electron emission
through thin insulating films. Tunnel effect also
explains the Zener breakdown in semiconductor
rectifiers. Tunnel effect is responsible for Josephson
effect.
THE UNCERTAINTY PRINCIPLE

 The uncertainty principle was formulated by Werner

Heisenberg in 1927. It states that it is impossible to
know both the exact position and exact momentum of
an object at the same time. Quantitatively it can be
written as Δ x. Δp x ≥ ħ/2 .This equation states that the
product of the uncertainty Δ x in the x-component of
position of an object and the uncertainty Δp x in the
corresponding momentum component at the same
instant is equal to or greater than ħ/2.
 Similar relations can be written for other pairs like
angular displacement Δθ and corresponding angular
momentum Jz. The relation is Δθ .ΔJ z ≥ ħ/2 .
 Also, we can write an uncertainty relation connecting
the variables time t and energy E in the form
 Δt .ΔE ≥ ħ/2
 Absence of electrons inside a
nucleus
 Typical nuclei have radii of the order of 10-15 m . Consider a
nucleus having radius 5 Fermi. For an electron to be
confined within such a nucleus, the uncertainty in its
position may not exceed 5 X 10-15 m, i.e., x = 5 X 10-15 m.
 The corresponding uncertainty in its momentum is
  p x = h/ 4 x x . = 5.2728 x 10-35 Js / 5 X 10-15 m

 = 1.054 x 10-20 kg.m/ s

 If this is the uncertainty in the momentum of the electron,

the momentum itself is of the order of this magnitude.
Hence,
 p x =1.054 x 10-20 kg.m/ s

 Its kinetic energy T must be much greater than its rest
energy m0c2. Hence we use the
 relativistic expression for kinetic energy, neglecting the rest
energy. Hence,
 T = pX c
 = 1.054 × 10-20 kg.m/s × 3 × 108 m/s
 = 3.162 × 10–12 J
 Since 1eV = 1.6 x 10-19 J, the kinetic energy of the electron
must be more than 19.76MeV , if it is to be a nuclear
constituent. Experiments indicate that the electrons
associated even with unstable atoms never have more than
a fraction of this energy, and we conclude that electrons
cannot be present within nuclei
Uncertainty in the Frequency of light
emitted by an atom

 Consider the radiation of light emitted by an excited

atom. Such an atom can stay in the excited state for
about 10-8 s. That is the uncertinty in the time of de
excitation is t = 10-8 s.
 The corresponding Uncertainty in energy is,
 ΔE = ħ/2 . t
 h. Δ = ħ/2 . t
 Δ = 1/ 4 t
 =7.96 x 106 Hz
 This means the emitted spectral line is not sharp, but
has some width. This broadening of spectral line
which cannot be reduces further is known as Natural
Line Broadening.
Numericals