Quantum Mechanics 2023

Unit II- Quantum Mechanics

Matter and Radiation are both forms of energy and are inter convertible, as established by
Einstein’s mass energy equivalence relationship, E =mc2. Electromagnetic radiation commonly
exhibits wavelike properties (interference, diffraction and polarization) and in certain cases (black body
radiation, photoelectric effect and Compton scattering) behaves like a stream of particles called
photons. The dual nature of electromagnetic radiation has led Louis de Broglie to propose that matter
should also have dual character and that particles such as electrons should also have wave like
properties.

de-Broglie hypothesis: A free particle moving with a linear momentum, 𝑝, is associated with a
sinusoidal wave of wavelength
 = 𝒉/𝒑 (𝑝 = 𝑚𝑣 , 𝑚 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑎𝑠𝑠 𝑎𝑛𝑑 𝑣 𝑖𝑠 𝑡ℎ𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒)
The wavelength  is called the de Broglie wavelength.

 For ordinary objects, the wave like behavior cannot be observed as Planck’s constant is very
small (≈ 10-34 Js).
 In the atomic or subatomic scale, the momentum can be sufficiently small to bring the de
Broglie wavelength into the observable range.
 The basic difference between a wave and a particle is that position of a particle can be localized
in time and space but a wave is spread out in both these dimensions.

Distinction between the expressions for energy of a photon and a particle

Photon is a mass less particle and for a photon 𝐸 = 𝑚𝑐 2 = 𝑝𝑐
(𝑚𝑐 = 𝑝 𝑎𝑠 𝑡ℎ𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑖𝑠 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 𝑐)
𝑬 = 𝒑𝒄 = 𝒉𝒄⁄ for a photon
For a matter particle, the velocity is always less than the velocity of light and as the velocity approaches
the velocity of light the mass of the particle tends to∞ as seen from the relation,

Relativistic mass, 𝑚 = 𝑚0 ⁄√1 − (𝑣 2 ⁄𝑐 2 ) -----------------(i)

where 𝑚0 is the rest mass and 𝑚 is the mass corresponding to a velocity v.
Squaring the equation (i) and rearranging the terms, we obtain
𝑚2 [𝑐 2 − 𝑣 2 ] = 𝑚0 𝑐 2 -------------------(ii)
1
Quantum Mechanics 2023

Multiplying on both sides with 𝑐 2 we get,

𝑚2 𝑐 4 – 𝑚2 𝑐 2 𝑣 2 = 𝑚02 𝑐 4
or 𝐸 2 = 𝐸02 + 𝑝2 𝑐 2
Therefore, energy of a relativistic matter particle, 𝑬 = √𝑬𝟐𝒐 + 𝒑𝟐 𝒄𝟐
For a particle whose velocity, 𝒗 < < 𝑐, (non-relativistic particle) , 𝒎 = 𝒎𝟎
𝟏
and 𝑬 = 𝟐 𝒎𝒗𝟐 = 𝒑𝟐 ⁄𝟐𝒎

Phase velocity: Phase velocity is the velocity with which a phase point located on a progressive wave
is transported.
Phase velocity is the same as the wave velocity. 𝑉𝑃 = ν ( is the frequency)
P

Let P be a phase point located on a Travelling wave represented by the equation

𝑦 = 𝐴𝑠𝑖𝑛(𝑘𝑥 − 𝜔𝑡)
𝑘 = 2𝜋⁄ is the wave number and 𝜔 = 2𝜋 is the angular frequency
 is the wavelength of the wave and  is the frequency.

The velocity of the phase point will be the same as the wave velocity and can be given as
𝜔 2𝜋 𝜔
𝑉𝑃 =   = 2𝜋 . = ⋯⋯⋯⋯(i)
𝑘 𝑘

Also,  = 𝐸 ⁄ℎ and 𝐸 = 𝑚𝑐 2 ⋯ ⋯⋯ (ii)

 = ℎ⁄𝑝 and 𝑝 = 𝑚𝑣 ⋯⋯⋯⋯(iii)
𝐸
Substituting (ii) and (iii) in (i), we obtain 𝑉𝑃 = 𝑝 = 𝑐 2 ⁄𝑣

𝑣 is the velocity of the particle. For photons (light quanta), v =c in vacuum and hence phase
velocity is equal to velocity of light. Particles like electrons travel with velocities less than c and so
phase velocity of matter waves 𝑉𝑃 > 𝑐 which has no physical significance. For a physical
representation of matter waves, we require to consider a wave packet to be associated with the moving
body.

2
Quantum Mechanics 2023

Group velocity
A wave group is formed due to superposition of waves of different wavelengths whose interference
with one another results in variation of amplitude.

Wave packet

Y1
+ =

Y2

Expression for group velocity

Consider two waves of same amplitude A but slightly different wave numbers and angular frequencies
represented by the equations,
𝑦1 = 𝐴 𝑠𝑖𝑛(𝑘𝑥 − 𝜔𝑡) and 𝑦2 = 𝐴 𝑠𝑖𝑛[(𝑘 + ∆𝑘)𝑥 − (𝜔 + ∆𝜔)𝑡] ---------------(i)

The resultant of the superposition of these two waves can be written as,
∆𝑘𝑥 ∆𝜔𝑡 2𝑘+∆𝑘 2𝜔+∆𝜔
𝑦 = 𝑦1 + 𝑦2 = 2𝐴𝑐𝑜𝑠 ( − ) 𝑠𝑖𝑛 [( )𝑥 − ( ) 𝑡] -------------------------(ii)
2 2 2 2

Substituting, 2𝑘 + ∆𝑘 ≈ 2𝑘 and 2𝜔 + ∆𝜔 ≈ 2𝜔
∆𝑘𝑥 ∆𝜔𝑡
𝑦 = 2𝐴𝑐𝑜𝑠 ( − ) sin(𝑘𝑥 − 𝜔𝑡)-------------------(iii)
2 2

The above equation represents a sine wave of angular frequency ω and wave number 𝑘 whose
amplitude is modulated with the angular frequency ∆ω/2 and wave number ∆𝑘/2.
Group velocity is defined as the rate at which the amplitude is modulated or the rate at which energy
is transported or the velocity of motion of the wave packet
From eqn. (iii) the rate of modulation of amplitude, 𝑉𝑔 = ∆𝜔⁄∆𝑘 = 𝑑𝜔⁄𝑑𝑘

2𝜋
𝑑𝜔 = 2𝜋. 𝑑 = 2𝜋𝑑(𝐸⁄ℎ) and 𝑑𝑘 = = 2𝜋. ℎ/𝑝
𝑑

 Vg = dω⁄dk = dE/dp

The wave packet consists of regions of constructive and destructive interference. The probability of
finding the particle in a given region depends on the amplitude of the wave group in that region. The
3
Quantum Mechanics 2023

wave group representation enables the localization of the particle. The motion of the wave group, not
the motion of individual waves that make up the wave group, corresponds to the motion of the body.
We can prove that group velocity of the wave packet is the same as the velocity of the particle.

To show that group velocity is equal to velocity of the particle

𝑉𝑔 = 𝑑𝜔⁄𝑑𝑘 = 𝑑𝐸/𝑑𝑝

𝐸 = 𝑝2 ⁄2𝑚 and 𝑑𝐸 = 2𝑝. 𝑑𝑝⁄2𝑚

𝑑𝐸 𝑝 𝑚𝑣
= = =𝑣
𝑑𝑝 𝑚 𝑚

 𝑽𝒈 = 𝒗

Relationship between phase velocity and group velocity

Depending on how the phase velocity varies with wavelength, the group velocity may be less
or greater than the phase velocities of the member waves. If the phase velocity is independent of wave
length, it is a nondispersive medium. Variation of phase velocity with wavelength is called dispersion.
We can obtain the relationship between group and phase velocities in a dispersive medium in the
following way:
𝝎
𝑉𝑷 = 𝒐𝒓 𝒌. 𝑽𝑷 = 𝝎 ---------(i)
𝒌

𝑑𝑉𝑃 𝑑𝜔
Differentiate w.r.t. 𝑘 to obtain, 𝑉𝑃 + 𝑘 = = 𝑉𝑔 -------(ii)
𝑑𝑘 𝑑𝑘
2𝜋
𝑘= ------(iii)


and 𝑑𝑘 = −2𝜋. 𝑑⁄2 -------(iv)

substituting (iii) and (iv) in (ii) we obtain,

𝒅𝑽𝑷
𝑽𝒈 = 𝑽𝑷 −  ( )
𝒅
which relates phase and group velocities in a dispersive medium.

dV
Note: In case of non-dispersive medium, all wavelengths travel with same velocity. i.e. ( dP ) = 0. In

such case, 𝐕𝐠 = 𝐕𝐏 .

4
Quantum Mechanics 2023

Heisenberg’s Uncertainty Principle

Statement: It is not possible to determine simultaneously and with unlimited precision, a pair of
conjugate variables like position and momentum of a particle.
Heisenberg’s uncertainty relationships:
∆𝑥. ∆𝑝 ≥ ℎ⁄4𝜋
∆𝜃. ∆𝐿 ≥ ℎ⁄4𝜋
∆𝑡. ∆𝐸 ≥ ℎ⁄4𝜋
Heisenberg’s uncertainty principle is a natural consequence of wave nature of matter.
When we consider the particle as a wave group there are fundamental limits to the accuracy with
which we can determine the particle properties like position and momentum,
Let us consider an individual wave which can extend from 𝑥 = −∞ 𝑡𝑜 𝑥 = +∞. This wave has a
precisely defined wavelength and consequently, a precisely determined wave number and momentum.
So, the uncertainty in the momentum ∆𝑝 = 0 which implies that the momentum can be precisely
determined in case of a single wave. However, the amplitude of the wave is the same at all points from
𝑥 = −∞ 𝑡𝑜 𝑥 = +∞. and the uncertainty in determining the position ∆𝑥 = ∞ .
In order to localize the particle and reduce the uncertainty ∆𝑥 from ∞ to a finite value we
have to consider a wave group of different wavelengths and this introduces uncertainty in wave number
and hence the momentum. A large number of waves will result in lesser ∆𝑥 and higher value of ∆𝑝
and vice versa.

A more rigorous Fourier analysis of the waves will give us the relationship
∆𝒙. ∆𝒑 ≥ 𝒉⁄𝟒𝝅

5
 Quantum Mechanics 2023

Applications of Heisenberg’s uncertainty principle

Applying the Heisenberg’s uncertainty principle, we can show that electrons cannot exist within
the atomic nucleus.
Proof:
The diameter of an atomic nucleus is ≈ 5 x10-15m. If an electron is inside the atomic
5×10-15m
nucleus, the uncertainty in determining its position, ∆x =5 x10-15m.
The uncertainty in determining its momentum, ∆p =ℎ⁄4𝜋. ∆𝑥
=6.6 × 10−34 ⁄4 × 3.14 × 5 × 10−15
= 1.05 × 10−20 kg m s-1
But, the momentum must be greater than the uncertainty in it
ie., 𝑝 ≥ ∆p, or, p = 1 . 05 × 10−20 kg m s-1
The energy of the electron can be calculated from the expression, 𝐸 = √𝐸𝑜2 + 𝑝2 𝑐 2

𝐸 = √{9.1 × 10−31 × (3 × 108 )2 }2 + {(1.05 × 10−20 )2 × (3 × 108 )2 }

=20 MeV
If an electron has an energy of 20 MeV, it will escape from the nucleus since the binding energy of a
nucleon is approximately 3 or 4 MeV. Hence an electron cannot be confined within the atomic nucleus.

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.
𝑥=+∞
∫𝑥=−∞ 𝛹(𝑥)∗ 𝛹(𝑥)𝑑𝑥 = 1 , in one dimension or
∭ 𝛹(𝑟)∗ 𝛹(𝑟)𝑑𝑟 = 1 where 𝑟 = 𝑥𝑖 + 𝑦𝑗 + 𝑧𝑘 represents the position r in three dimensions.

6
Quantum Mechanics 2023

Max. Born’s Interpretation of wave function

In 1926, Max Born attempted to relate the properties of the wave function Ψ (x,t) and the
behaviour of the associated particle which is expressed in terms of the probability density P(x,t). This
quantity specifies the probability per unit length of the x axis, of finding the particle near the
coordinate x at time t. According to this postulate, 𝑃(𝑥, 𝑡) = 𝛹 ∗ (𝑥, 𝑡)𝛹(𝑥, 𝑡)

Where 𝛹 ∗ (𝑥) is the complex conjugate of 𝛹(𝑥, 𝑡)

If, at the instant t, a measurement is made to locate the particle associated with the wave
function 𝛹(𝑥, 𝑡), then the probability P(x,t) dx that the particle will be found at a coordinate between

x and x + dx is equal to 𝛹 ∗ (𝑥, 𝑡)𝛹(𝑥, 𝑡)𝑑𝑥.

Schrodinger’s time independent wave equation in one dimension

The classical wave equation that describes any type of wave motion can be given as

𝜕 2 𝑦(𝑥, 𝑡) 1 𝜕 2 𝑦(𝑥, 𝑡)
= 2
𝜕𝑥 2 𝑣 𝜕𝑡 2
Where y is a variable quantity that propagates in ‘x ‘ direction with a velocity ‘v’.
Matter waves should also satisfy a similar equation and we can write the equation for matter waves as

𝜕2 𝛹(𝑥,𝑡) 1 𝜕2 𝛹(𝑥,𝑡)
= ⋯ ⋯ (𝑖)
𝜕𝑥 2 𝑣2 𝜕𝑡 2

We can eliminate the time dependence from the above equation by assuming a suitable form of the
wave function and making appropriate substitutions.

Let 𝛹(𝑥, 𝑡) = 𝛹0 (𝑥)𝑒 −𝑖𝜔𝑡 ⋯ ⋯ ⋯ ⋯ ⋯ (𝑖𝑖)

where, 𝛹0 (𝑥)depends only on ‘x,’ and 𝑒 −𝑖𝜔𝑡 depends only on ‘t ′ .

Differentiate eqn. (ii) w.r.t. ‘x’ successively to obtain

𝜕𝛹(𝑥, 𝑡) 𝑑𝛹0 (𝑥) −𝑖𝜔𝑡
= 𝑒 and
𝜕𝑥 𝑑𝑥
𝜕 2 𝛹(𝑥, 𝑡) 𝑑 2 𝛹0 (𝑥) −iωt
= e ⋯ ⋯ ⋯ (iii)
𝜕𝑥 2 𝜕𝑥 2
7
Quantum Mechanics 2023

Differentiate eqn.(ii) w.r.t. ‘t’ to obtain

𝜕𝛹(𝑥, 𝑡)
= (−𝑖𝜔)𝛹0 (𝑥)𝑒 −𝑖𝜔𝑡 )
𝜕𝑡
𝜕 2 𝛹(𝑥, 𝑡)
2
= (−𝑖𝜔)2 𝛹0 (𝑥)𝑒 −𝑖𝜔𝑡 ⋯ ⋯ ⋯ (𝑖𝑣)
𝜕𝑡
Substituting (iii) and (iv) in eqn. (i), we obtain
𝑑 2 𝛹0 (𝑥) −iωt ω2
e = − 2 𝛹0 (𝑥)𝑒 −𝑖𝜔𝑡 ⋯ ⋯ (𝑣)
𝜕𝑥 2 v
We can cancel 𝑒 −𝑖𝜔𝑡 on both sides to eliminate time dependence and get
𝑑2 𝛹0 (𝑥) ω2
= − 𝛹 (𝑥) = −𝑘 2 𝛹0 (𝑥) ⋯ ⋯ (𝑣𝑖)
𝜕𝑥 2 v2 0
𝑑2 𝛹0 (𝑥)
or + 𝑘 2 𝛹0 (𝑥) = 0 ⋯ ⋯ (𝑣𝑖𝑖)
𝜕𝑥 2
2𝜋 ℎ 4𝜋 2 𝑝2
𝑘= and = , ∴ 𝑘2 =
 𝑝 ℎ2

The energy of the particle,’E’ is the sum of kinetic and potential energy
𝑝2
𝐸= +𝑉 or 𝑝2 = 2𝑚(𝐸 − 𝑉) or 𝑘 2 = 8𝜋 2 𝑚(𝐸 − 𝑉) /ℎ2
2𝑚
Substituting the value of 𝑘 2 and replacing 𝛹0 (𝑥)by Ψ (x) in eqn.(vii) , we obtain the Schrodinger’s
time independent wave equation in one dimension as:
𝒅𝟐 𝜳(𝒙) 𝟖𝝅𝟐 𝒎(𝑬 − 𝑽)
+ 𝜳(𝒙) = 𝟎
𝒅𝒙𝟐 𝒉𝟐
The above equation can be solved for different cases to obtain the allowed values of energy
and the allowed wave functions.

Particle in an infinite one-dimensional potential well

Consider a particle of mass ‘m’ confined to a one-dimensional potential well

of dimension ‘L’. The potential energy, V = ∞ at x=0 and x= L and V = 0 for
0≤ x ≤ L . The walls are perfectly rigid and the probability of finding the particle
is zero at the walls.
Hence, the boundary conditions are , Ψ(x ) = 0 at x=0 and x= L . 𝑉=∞

8
Quantum Mechanics 2023

The one-dimensional time independent wave equation is

d2 Ψ(x) 8π2 m(E−V)
+ Ψ(x) = 0
dx2 h2
We can substitute V=0 since the particle is free to move inside the potential well.
𝑑 2 𝛹(𝑥) 8𝜋 2 𝑚𝐸
we obtain , + 𝛹(𝑥) = 0
𝑑𝑥 2 ℎ2
8𝜋 2 𝑚𝐸
Let 2
= 𝑘 2 and the wave equation is,
ℎ
𝑑 2 𝛹(𝑥)
+ 𝑘 2 𝛹(𝑥) = 0
𝑑𝑥 2
The above equation represents simple harmonic motion and the general solution is
𝛹(𝑥) = 𝐴 𝑠𝑖𝑛 𝑘𝑥 + 𝐵 cos 𝑘𝑥
Applying the condition, 𝛹(𝑥) = 0 𝑎𝑡 𝑥 = 0, we get
0 = 𝐴. 0 + 𝐵 which implies that B =0
Substituting the condition 𝛹(𝑥) = 0 𝑎𝑡 𝑥 = 𝐿, we get, 𝐴 sin 𝑘𝐿 = 0
𝐴 ≠ 0 which implies that sin 𝑘𝐿 = 0
The quantization condition is
𝑘𝐿 = 𝑛𝜋
or, 𝑘 = 𝑛𝜋⁄𝐿 where 𝑛 = 1,2,3 ⋯ ⋯ is a positive integer.

Eigen values of energy:

𝑘 2 ℎ2 𝑛2 𝜋 2 ℎ2
𝐸𝑛 = =
8𝜋 2 𝑚 8𝜋 2 𝑚𝐿2
n2 h2
En =
8mL2
‘n’ is the quantum number corresponding to a given energy level.
n=1 corresponds to the ground state, n=2 corresponds to the first excited state and so on.

Eigen functions: The allowed wave functions are

𝛹𝑛 (𝑥) = 𝐴 𝑠𝑖𝑛(𝑛𝜋𝑥 ⁄𝐿)
The constant A can be evaluated from normalization condition,
𝑥=𝐿
∫ 𝐴2 𝑠𝑖𝑛2 (𝑛𝜋𝑥 ⁄𝐿) = 1
𝑥=0

9
Quantum Mechanics 2023

using the trigonometric identity 𝑠𝑖𝑛2 𝜃 = (1 − 𝑐𝑜𝑠2𝜃)/2

2𝜋𝑛𝑥
1 − 𝑐𝑜𝑠( 𝐿 )
𝐿
we get 𝐴2 ∫ ( ) 𝑑𝑥 = 1
0 2

𝐿
𝐴2 𝐿
after integration we obtain, [𝑥 – 𝑠𝑖𝑛(2𝑛𝜋𝑥 ⁄𝐿)] = 1
2 2𝑛𝜋 0

𝐴2 𝐿 2
or = 1 or A=√
2 𝐿

Hence, the Eigen functions are,

2 𝑛𝜋
Ψn (x) = √ Sin ( 𝑥)
L 𝐿
Probability densities: The probability of finding the particle in a small region ‘dx’ in a given quantum
state ‘n’ is
2
𝑠𝑖𝑛2 (𝑛𝜋𝑥 ⁄𝐿)𝑑𝑥
𝑃𝑛 (𝑥) =
𝐿
𝑥2 𝑥2
2
or, ∫ 𝑃𝑛 (𝑥)𝑑𝑥 = ∫ 𝑠𝑖𝑛2 (𝑛𝜋𝑥 ⁄𝐿) 𝑑𝑥
𝑥1 𝑥1 𝐿

Graphical representation of 𝐸𝑛 , 𝛹𝑛 (𝑥)and 𝑃𝑛 (𝑥) for n = 1,2 and 3 quantum states

Eigen values Eigen functions Probability densities 𝑃𝑛 (𝑥)

𝑛2 ℎ 2 2
𝐸𝑛 = 8𝑚𝐿2 𝛹𝑛 (𝑥) = √2⁄𝐿 𝑠𝑖𝑛(𝑛𝜋𝑥 ⁄𝐿) 𝑃𝑛 (𝑥) = 𝐿 𝑠𝑖𝑛2 (𝑛𝜋𝑥 ⁄𝐿)𝑑𝑥

10