Module 2

Quantum Mechanics
Wave Particle dualism (Dual nature)

Any physical entity either matter or radiation which exhibits wave nature under certain
experimental conditions and particle nature in some other experimental conditions is known
as the concept of wave particle dualism or dual nature or dual characteristics.

de-Broglie hypothesis
Dual nature of radiation: - the phenomena of interference, diffraction and polarization of light
could be explained on the basis of wave nature of electromagnetic radiation or light. Similarly
black body radiation spectrum, photoelectric effect and Compton scattering could be explained
on the basis of particle nature of radiation of light or EM wave. Hence light or EM radiation
exhibits dual nature under different experimental situations.
Dual nature of matter: - in 1924 de-Broglie on the similarities observed in nature suggested
that when radiation exhibits dual nature, then similarly matter or material particles like
electrons, protons, neutrons, nucleus, atoms and molecules also exhibits dual nature that is
wave and particle nature under different experimental conditions. So that matter also like
radiation exhibits dual characteristics under appropriate experimental conditions.
de-Broglie wavelength
Matter waves definition: - The waves associated with a material particle in motion are called
matter waves. Which also known as de-Broglie wavelength.
Expression for de-Broglie wave length of matter waves
de-Broglie derived an expression for the wave length associated with a material particle similar
to EM radiation.
According to Plank’s quantum theory of radiation the energy of photon (particle) is given by
E = hν = hc/λ (1)
Where E is the energy of photon, h is the Plank’s constant, c is the velocity of light, λ is the
wave length of EM wave.
According to Einstein's mass energy relation E = mc2 (2)
Where E is the energy of light particle, m is the mass of light particle and c is the velocity of
light particle, from equations 1 and 2
mc2= hc/λ

Which implies that λ = h/mc = h/p (3)

Let an electron of mass m is moving with velocity v and momentum p is given by

p = mv (4)
Substitute equation 4 in 3 then we get

ℎ ℎ
𝜆= =𝑝 (5)
𝑚𝑣

Which is the expression for de-Broglie wave length for matter waves associated with material
particle.

de-Broglie wave length of matter waves associated for an accelerated charged particles is
given by

ℎ ℎ ℎ
𝜆= = =
𝑝 √2𝑚𝐸 √2𝑚𝑒𝑉0

Where E is the kinetic energy of accelerated material particle eV0 is the accelerated potential
energy.

Phase Velocity

Definition: If point is imagined to be marked on a travelling wave, then it becomes a

representative point for a particular phase of the wave, and the velocity with which it is
transported owing to the motion of the wave, is called the phase velocity of the wave pocket.
𝜔
It is given by the equation 𝑣𝑝ℎ𝑎𝑠𝑒 = 𝑚/𝑠
𝑘

Group velocity

Definition: it is the velocity with the envelope of enclosing a wave group formed due to
superposition of two or more travelling waves of slightly different wavelengths is transported
is called group velocity.

𝑑𝜔
It is given by the equation 𝑣𝑔𝑟𝑜𝑢𝑝 = 𝑚/𝑠
𝑑𝑘

Heisenberg's uncertainty principle and its physical significance

Statement Heisenberg’s uncertainty principle: - it is impossible to determine precisely and

simultaneously the values of the both the members of a pair of physical variables which
describe the motion of an atomic system. Such pair of physical variables are called canonically
conjugate physical variables.

Explanation: - Let Δx and Δp are the errors in the measurement of position and linear
momentum, ΔE and Δt are the errors in the measurement of energy and time and ΔL and Δθ
are errors in the measurement of angular momentum and angular displacement. The above pairs
of physical variables are called canonically conjugate physical variables which describing the
motion of the atomic system. The uncertainty principle extended to the above three pairs of
canonically conjugate physical variables as follows,

In any simultaneous measurement of the canonically conjugate physical variables of the

physical system (either matter or radiation), the product of corresponding uncertainties
inherently present in the measurement and is equal to or greater than h/4π mathematically is
given by

Δx . Δpx ≥ h/4π

ΔE . Δt ≥ h/4π

ΔL . Δθ ≥ h/4π

Physical significance

Heisenberg uncertainty principle has physical significance because it is measurable and can be
applicable to find the (i) It can be possible to prove that the product of uncertainties in the
measurement of two canonically conjugate Physical variables is approximately equal to Plank’s
constant (ii) determination of position of electron inside the atom (iii) nonexistence of electrons
inside the nucleus.

Application of Heisenberg uncertainty principle (Physical significance)

Nonexistence electron inside the nucleus: - If the electron existing inside the nucleus then the
uncertainty in its position Δx must not exceed the size of nucleus. The size of the nucleus is of
the order of x = 10-14 m. Because the diameter of the nucleus is of the order of 10-14m. Hence
electron to exists inside the nucleus Δx ≤ x.

According to uncertainty principle Δx . Δpx ≥ h/4π

ℎ 6.62 × 10−34
Δp𝑥 ≥ = = 0.52 𝑥10−20 𝑁𝑠
4𝜋∆𝑥 4𝑥3.142 𝑥 10 −14

Hence ΔP = 0.5 𝑥10−20 𝑁𝑠 is the uncertainty in the value of momentum of [Link] principle
if the electron is existing inside the nucleus the momentum of the electron must equal to
uncertainty in momentum.

Hence P = ΔPx ≥ 0.52 𝑥10−20 𝑁𝑠 (1)

We know the rest mass of the electron, m0 = 9.11x10-31kg.

𝑝2
Consider the nonrelativistic energy and momentum equation that is 𝐸 = 2𝑚 (2)

Now introduce the Heisenberg uncertainty principle in the above equation and, that if electron
do exist inside the nucleus it has satisfy the condition,

𝑝2
𝐸 ≥ 2𝑚 (3)

The energy of the electron can be calculated from the above equation by substituting the
momentum and mass of the electron.
 (0.52 𝑥10−20 )2 1.372×10−11
𝐸 = 2× 9.11×10−31 = 1.372 × 10−11 𝐽 = = 85 𝑀𝑒𝑉
1.602×1019

𝐸 ≥ 85 𝑀𝑒𝑉

𝐸 ≥ 85 𝑀𝑒𝑉 (4)

Which means that the electron do exists inside the nucleus its kinetic energy E must be greater
than or equal to85 𝑀𝑒𝑉. But experimental evidences on β decay reveals that the kinetic energy
of β particles (which are electrons) is the order of 3 to 4 MeV. Hence this clearly indicates that
the electrons cannot exists inside the nucleus.

Principle of complementarity correlation between the de-Broglie wavelength

In 1928 Neil Bohr introduced the complimentary principle and states that “in any experimental
situation in which a physical entity (matter or radiation) exhibits its wave properties, it is
impossible to attribute corpuscular characteristics to it”

The entity does behave like a particle if its wave pocket is made compact enough but when it is
done, it loses the ability to display any wave properties. In other words the particle wave
aspects of physical entity are complimentary and cannot be exhibited at the same time.

ℎ ℎ
𝜆=𝑝=
√2𝑚(𝐸−𝑉(𝑥))

Heisenberg’s Uncertainty principle and wave packet

Consider a wave pocket represented by wave function 𝜓(𝑥, 𝑡) which, at that instant t, has a
maximum at the point X(t).we will suppose for convenience that the function 𝜓 falls
monotonically as it moves to either side of the maximum position. If the position of the wave
pocket changes with time, the rate at which the maximum point moves is clearly a good
measure of the group velocity
𝑑𝑋(𝑡)
𝑣𝑔 = 𝑑𝑡
The wave pocket is composed of harmonic waves having a certain range of wavelengths, given
by
+⋈
𝜓(𝑥, 𝑡) = ∫−⋈ 𝑎(𝑘)𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑑𝑘
If the momentum is precisely specified we have no wave pocket at all, but only pure harmonic
wave, so that the particle position is completely unknown. But as per as Heisenberg uncertainty
principle there is inverse relationship between the accuracies to which the position and
momentum can be simultaneously specified. ∆𝑥. ∆𝑝𝑥 ≥ ℏ This inequality is the essential
content of the Heisenberg uncertainty principle. In case of 3D wave pocket is given by
+⋈
𝜓(𝑥, 𝑡) = ∫−⋈ 𝑎(𝑘)𝑒 𝑖(𝒌𝒙−𝜔𝑡) 𝑑3 𝑘

With the three uncertainty relations

∆𝑥. ∆𝑝𝑥 ≥ ℏ, ∆𝑦. ∆𝑝𝑦 ≥ ℏ and ∆𝑧. ∆𝑝𝑧 ≥ ℏ

Wave function

Definition of wave function: - any mathematical function which satisfies the properties of wave
function and Schrodinger wave equation whose solutions that explains the possible matter
waves associated with moving particle is called wave function.

Generally the wave function is represented by the symbol ψ and its complex conjugate by ψ*.
The de-Broglie or matter waves are complex in nature, hence complex mathematical functions
are selecting to represent waves associated with a material particle.

Mathematically the wave function for free particle is given by 𝜓 (𝑥 , 𝑡) = 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡)

And its complex conjugate is given by 𝜓 (𝑥 , 𝑡) = 𝜓0 𝑒 −𝑖 (𝑘𝑥 − 𝜔𝑡)

Physical significance: - The wave function be either real or complex and it has no physical
significance because it is not a measurable quantity. It explains the probability that a particle
will be found at a given place in space at a given instant of time and it is characterised by ψ (x,
y, z, t), where x, y and z are position coordinates and t is time coordinate.

Probability density: - It has physical significance because it is measurable quantity. It explains

the probability of finding the material particle associated with matter waves at particular
position, at given time in a given region of space. It is given by

𝑃 = |𝜓|2 = |𝜓 ∗ 𝜓| = |𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) × 𝜓0 𝑒 −𝑖 (𝑘𝑥 − 𝜔𝑡) | = |𝜓0 |2

𝑃 = |𝜓0 |2

Normalisation of wave function: - The integral of the square of the magnitude of the wave
function or probability density within a given volume and given limits is equal to 1. And the
wave function is called normalised wave function mathematically is given by,
+⋈ +⋈
𝑁= ∭ |𝜓|2 𝑑𝜏 = ∭ 𝑃 𝑑𝜏 = ∭ |𝜓|2 𝑑𝜏 = 1
−⋈ −⋈ 𝑤𝑖𝑡ℎ𝑖𝑛 𝑔𝑖𝑣𝑒𝑛 𝑙𝑖𝑚𝑖𝑡𝑠

Where d τ = is volume element =[Link]

Properties of wave function (general admissibility conditions)

1. The wave function should be single valued every where

2. The wave function should be finite every where
3. The wave function and its first derivatives are continuous functions of position and time
variables
4. For bound states the wave function vanish at infinite i.e. ψ and ψ* are complex conjugate
to each other then|ψ*ψ| Vanish at infinity.

Note :- Any mathematical function either algebraic function or exponential function, or

trigonometric function or logarithmic function which satisfying the above properties should be
selected as wave function to describe matter waves associated with moving material particle.
Time independent Schrödinger wave equation (Derivation)

The general differential equation for a wave travelling in positive x-direction with a wave
velocity u and wave function ψ is given by

𝑑2 𝜓(𝑥, 𝑡) 1 𝑑2 𝜓(𝑥,𝑡)
= (1)
𝑑𝑥 2 𝑢2 𝑑𝑡 2

In the above equation the wave function ψ is a function of position and time coordinates. The
wave function for a de-Broglie waves associated with moving particle along positive x-
direction can be written in complex form as follows,

𝜓 (𝑥 , 𝑡) = 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) (2)

Differentiate the above equation w.r.t. time t twice then we get

𝑑𝜓
= (−𝑖 𝜔)𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡)
𝑑𝑡

𝑑2𝜓
= (−𝑖 𝜔)(−𝑖 𝜔) 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡)
𝑑𝑡 2
𝑑2 𝜓
= − 𝜔2 𝜓 (3)
𝑑𝑡 2

Substitute the equation 3 in 1 to eliminate time then we get

𝑑2𝜓 1
2
= 2 (− 𝜔2 𝜓 )
𝑑𝑥 𝑢
𝑑2 𝜓 − 𝜔2
= 𝜓
𝑑𝑥 2 𝑢2

𝑑2 𝜓 𝜔2
+ 𝜓=0 (4)
𝑑𝑥 2 𝑢2

In which equation ψ is function of position only.

𝑢 2𝜋𝑢 𝜔 2𝜋 𝑃 𝜔2 4𝜋 2 𝑃 2
We know that 𝜔 = 2𝜋𝜈 = 2𝜋 = ℎ⁄ = ⇉ = ⇉ = (5)
𝜆 𝑝 𝑢 ℎ 𝑢2 ℎ2

The total mechanical energy of the particle E is equal to sum of the kinetic energy and potential
1 𝑃2
energy that is given by T. E. = 𝐸 = 𝑚 𝑣2 + 𝑉 ⇉ 𝐸 = +𝑉
2 2𝑚

From the above equation we get 𝑃2 = 2𝑚 (𝐸 − 𝑉) (6)

Substitute equation 6 in 5 then we get

𝜔2 4𝜋 2 (2𝑚 (𝐸−𝑉)) 8𝜋 2 𝑚(𝐸−𝑉) 2𝑚(𝐸−𝑉)

= = = (7)
𝑢2 ℎ2 ℎ2 ℏ2
Substitute equation 7 in 4 then we get

𝑑2 𝜓 2𝑚(𝐸−𝑉) 𝑑2 𝜓 8𝜋 2 𝑚(𝐸−𝑉)
+ 𝜓=0 Or + 𝜓=0 (8)
𝑑𝑥 2 ℏ2 𝑑𝑥 2 ℎ2

Which is the required one dimensional time independent Schrodinger wave equation.

The above equation can be extended to three dimensional as follows

2𝑚(𝐸−𝑉) 8𝜋 2 𝑚(𝐸−𝑉)
𝛻2𝜓 + 𝜓=0 Or 𝛻2𝜓 + 𝜓=0 (9)
ℏ2 ℎ2

𝛿2 𝛿2 𝛿2
Where 𝛻 2 = 𝛿𝑥 2 + 𝛿𝑦 2 + 𝛿𝑧 2 which is Laplacian differential operator in three dimension

Eigenvalues and Eigen functions

Brief explanation of Operator formalism of quantum mechanics

Eigen function: - Any wave function which should satisfying the general Eigen value equation
𝐴̂𝑜𝑝 𝜓 = 𝜆 𝜓 is known as Eigen function. Where 𝐴̂𝑜𝑝 is any mathematical operator
corresponding to particular dynamical variable, ψ is wave function corresponding to the
operator 𝐴̂𝑜𝑝 and λ is the Eigen value of the operator.

Eigen values: - The mathematical operators corresponding to particular physical variable or

observable operating on an eigen function or wave function furnish eigen values. The Eigen
values are the constants obtained from eigen value equation for particular physical observable
which in turn explains the state of the quantum mechanical system.

Note: - One eigen function can be selected for the entire one physical system and different
operators operating to obtain eigen values corresponding to different operators.

Mathematical Operator: - A mathematical operator is a symbol or code which directs one to

perform a particular mathematical operation on the wave function or eigen function.

In quantum mechanics for each type of measurement of particular physical quantity there exists
one kind of operator. For example to obtain momentum values of a quantum particle,
momentum operator operates on eigen function, to obtain energy values there is energy
operator operates on eigen function.

General mathematical operator

Operator Mathematical Operation

Symbol

±, ×, ÷ Addition, subtraction and

multiplication operation

√ , Square root operation

 Integration
∫

𝑑 Differentiation operation with

𝑑𝑥 respect to x

Quantum mechanical mathematical operator

Physical variable or Operator Symbol for

observables operator

position x 𝑥̂

Momentum −𝑖ℏ𝛻 𝑃̂
𝛿 𝛿 𝛿
Where 𝛻 = 𝛿𝑥 + 𝛿𝑦 + 𝛿𝑧

kinetic energy ℏ2
− 2𝑚 𝛻 2 𝑇̂

𝛿2 𝛿2 𝛿2
𝛻 2 = 𝛿𝑥 2 + 𝛿𝑦 2 + 𝛿𝑧 2 which is
Laplacian differential operator in
three dimension
Total energy ℏ2
𝐸 = − 2𝑚 𝛻 2 + 𝑉
̂
𝐻

In quantum mechanics the general eigen value equation is given by 𝐴̂𝑜𝑝 𝜓 = 𝜆 𝜓

Examples

𝑑
1. Let us select ψ = sin (3x) and 𝐴̂ = then as per as above eigen value equation when the
𝑑𝑥
𝑑 sin 3𝑥
differential operator operates on the given function that is = 3 cos 3𝑥 which implies
𝑑𝑥
𝑑
that 3 is not a eigen value of the operator 𝑑𝑥 . Because ψ = sin3x is not a eigen function,
hence general eigen value equation explains that mathematical operator after operation on
eigen function leaves the same eigen function multiplied by constant and which the above
𝑑2 sin 3𝑥
equation not satisfies. Let us take = −9 sin 3𝑥
𝑑𝑥 2

𝑑2
Differential operator, ψ = sin3x is the eigen function and -9 is the eigen value of the
𝑑𝑥 2
𝑑2
operator 𝑑𝑡 2 the above equation which satisfies the general eigen value equation.

𝑑𝑒 𝑎𝑥 𝑑2 𝑒 𝑎𝑥
2. 𝜓 = 𝑒 𝑎𝑥 That is 𝑑𝑥 = 𝑎𝑒 𝑎𝑥 and = 𝑎2 𝑒 𝑎𝑥 both the equations are satisfying
𝑑𝑡 2
the general eigen value equation.
Example of calculation of momentum and energy eigen values of matter waves of free particle

𝑑
1. 𝜓 (𝑥 , 𝑡) = 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) 𝑃̂ = −𝑖 ℏ 𝛻 ⇉ 𝑃̂ = −𝑖ℏ 𝑖𝑛 𝑜𝑛𝑒 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛 as per as
𝑑𝑥
eigen value equation

𝑑𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡)

−𝑖ℏ = −𝑖 ℏ(𝑖𝑘)𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) = ℏ𝑘𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) = ℏ𝑘 𝜓
𝑑𝑥

Hence P = ℏ𝑘 is the momentum density of the matter waves a free particle.

2
̂ = − ℏ 𝛻2 +
2. . 𝜓 (𝑥 , 𝑡) = 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) Is the wave function of the free particle and 𝐻 2𝑚
𝑉 Is the total energy operator, because it is free particle for which V=0. Hence we
2 2 2
have𝐻̂ = − ℏ 𝛻 2 𝑎𝑛𝑑𝐻 ̂ = − ℏ 𝑑 2 𝑖𝑛 𝑜𝑛𝑒 𝑑𝑖𝑚𝑛𝑠𝑖𝑜𝑛.
2𝑚 2𝑚 𝑑𝑥

Hence as per as eigen value equation we have

ℏ2 𝑑2 𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) ℏ2 ℏ2 𝑘 2
− 2𝑚 = − 2𝑚 (𝑖𝑘 × 𝑖𝑘)𝜓0 𝑒 𝑖 (𝑘𝑥 − 𝜔𝑡) =
𝑑𝑥 2 2𝑚

ℏ2 𝑘 2 𝑃2
Which implies that Total energy = E = = which is the energy density of matter
2𝑚 2𝑚
waves associated by moving particle.

Particle in box

Application of Schrodinger’s wave equation: - To particle in a potential well of infinite wall

height

Energy eigen function and eigen value equation

Consider a particle moving inside a potential well of infinite depth or particle in box in positive
x – direction. The particle bouncing to fro between the walls of the box. The box has infinite
potential barriers at x = 0 and x= a as shown in figure. The particle has mass m and its position
at any instant lies 0 ≤ x ≤ a. The particle cannot exists outside the box. So its wave function ψ
= 0 at x ≤ 0 and x ≥ a means that particle can never existing outside the box. But the wave
function ψ (x) ≠ 0 within the box which means that particle always existing inside the box as
shown in figure.

Consider the Schrodinger time independent wave equation for particle in a box
𝑑2 𝜓 2𝑚(𝐸−𝑉)
+ 𝜓=0 (1)
𝑑𝑥 2 ℏ2

Inside the potential well the potential is constant (independent of time) hence V = 0 hence the
above equation 1 becomes

𝑑2 𝜓 2𝑚𝐸
+ 𝜓=0 (2)
𝑑𝑥 2 ℏ2

2𝑚𝐸
Put = 𝑘2 (3)
ℏ2

In the above equation the equation 1 become

𝑑2 𝜓
+ 𝑘2 𝜓 = 0 (4)
𝑑𝑥 2

The general solution of the differential equation 4 is given

𝜓𝑛 (𝑥) = 𝐴 𝑠𝑖𝑛 𝑘𝑥 + 𝐵 𝑐𝑜𝑠 𝑘𝑥 (5)

Where A and B are arbitrary constants, k is a wave vector. The values of A, B and k can be
obtained by imposing boundary conditions on the particle and by substituting the boundary
conditions in the above equation 5.

Case I: - if x =0 ψ (x) = 0 then equation 5 become

0 = 𝐴 sin 0 + 𝐵 𝑐𝑜𝑠 0 ⇉ 𝐵=0 (6)

Case II: - if x = a, ψ (a) = 0 and B = 0 (from equ. 6) substitute these in equation 5 then we get

0 = 𝐴 sin 𝑘𝑎 + 0 × 𝑐𝑜𝑠 𝑘𝑎 ⇉ 𝐴𝑠𝑖𝑛𝑘𝑎 = 0 𝑎𝑛𝑑 𝐴 ≠ 0

𝐵𝑒𝑐𝑎𝑢𝑠𝑒 𝑖𝑡 𝑖𝑠 𝑎𝑟𝑏𝑖𝑡𝑟𝑎𝑟𝑦 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ℎ𝑒𝑛𝑐𝑒

𝑛𝜋
sin 𝑘𝑎 = 0 ⟹ 𝑘𝑎 = 𝑛 𝜋 𝑎𝑛𝑑 𝑘 = (7)
𝑎

Substituting equs. 6 and 7 in 5 then we get

𝑛𝜋
𝜓𝑛 (𝑥) = 𝐴 sin 𝑥 (8)
𝑎

Which is the solution of the Schrodinger time independent one dimensional wave equation for
a particle in a potential well of infinite depth.

In equation 8, the arbitrary constant A is called as normalisation constant, which can be

obtained by normalising the wave function obtained in equ. 8.

As per as normalisation principle it is given by

 +⋈ +⋈ 𝑎
2 𝑛𝜋 2
∫ 𝑃 𝑑𝑥 = ∫ |𝜓 (𝑥)| 𝑑𝑥 = ∫ |𝐴 sin 𝑥| 𝑑𝑥 = 1
−⋈ −⋈ 0 𝑎

2 𝑎 (1 − cos
2𝑛𝜋
𝑎 𝑥) 𝑑𝑥 = 1
𝑎 2
𝑛𝜋 𝐴
∫ 𝐴2 sin 𝑥 𝑑𝑥 = 1 ⟹ ∫
0 𝑎 2 0 2

2𝑛𝜋 𝑎
2𝑛𝜋
𝐴2 𝑎 𝐴2 𝑎 (cos 𝑎 𝑥) 𝐴2 𝐴2 [sin 𝑎 𝑥]0
∫0
1 𝑑𝑥 − ∫0
𝑑𝑥 = 1 ⟹ [𝑥]𝑎0 − 2𝑛𝜋 =1
2 2 2 2 2
𝑎

In this equ. The second term leads to zero hence it leads to

𝐴2 𝐴2 2
(𝑎 − 0) = 1 ⇒ 𝑎 = 1 ⟹ 𝐴 = √𝑎 − − − −(9)
2 2

Substituting equ. 9 in 8 then we get

2 𝑛𝜋
𝜓𝑛 (𝑥) = √𝑎 sin 𝑥 − − − −(10) Where n = 1, 2, 3…….,⋈
𝑎

Which is an eigen function or wave function of a particle in a potential well of infinite depth.

Energy eigen value equation

Consider the equation 3

2𝑚𝐸
= 𝑘2
ℏ2

𝑛2 𝜋 2 ℎ2
In this equation substitute the value of 𝑘 2 = and ℏ2 =
𝑎2 (2𝜋)2

2𝑚𝐸 𝑛2 𝜋 2 2𝑚𝐸4𝜋 2 𝑛2 𝜋 2
Then we get ℎ2
= ⟹ =
𝑎2 ℎ2 𝑎2
4𝜋2

After simplification we get

𝑛2 ℎ 2
𝐸𝑛 = (11)
8𝑚𝑎2

Where n = 1, 2, 3,…., ⋈

Which is the energy eigen value expression for the particle in a potential well of infinite depth
or particle in box.

Ground state energy level

If n = 0 substitute in equation 10 and 11, both equations leads to Zero, hence n = 0 is not ground
2 𝜋 ℎ2
state or least energy state. If we substitute n =1 then we get 𝜓1 (𝑥) = √𝑎 sin 𝑎 𝑥 and 𝐸0 = 8𝑚𝑎2
hence n =1 is the ground state or least energy energy state of particle in a well of infinite depth.

Discussion of wave functions, probability densities and energy eigen values of particle in
box in different energy states

Consider the eigen function, energy eigen value and probability expressions for the particle in
box

2 𝑛𝜋
𝜓𝑛 (𝑥) = √𝑎 sin 𝑥 (1)
𝑎

𝑛2 ℎ 2
𝐸𝑛 = (2)
8𝑚𝑎2

2 𝑛𝜋
𝑃 = 𝑎 𝑠𝑖𝑛2 ( 𝑎 𝑥) (3)

From the above equations we can generate the wave functions, energy eigen values and
probability densities for a particle in a box in different energy states as follows,

Case 1: When n = 1 is the Least or ground state energy

2 𝜋
Then 𝜓0 (𝑥) = √𝑎 sin 𝑎 𝑥 (1)

ℎ2
𝐸0 = (2)
8𝑚𝑎2

2 𝜋
𝑃 = 𝑎 𝑠𝑖𝑛2 (𝑎 𝑥) (3)

For different values of x the values of wave function, probability densities can be obtained and
recorded in the table 1 and their behaviour plotted in the graph

[Link] x Ψ (x) P

1 0 0 0
2 a/2 2/a
√2⁄𝑎

3 a 0 0
Case II: - when n = 2: first excited state energy level or orbital

Then we have

2 2𝜋
𝜓1 (𝑥) = √𝑎 sin 𝑥 (1)
𝑎

4 ℎ2
𝐸1 = (2)
8𝑚𝑎2

2 2𝜋
𝑃 = 𝑎 𝑠𝑖𝑛2 ( 𝑎 𝑥) (3)

For different values of x the values of wave function, probability densities can be obtained and
recorded in the table 2 and their behaviour plotted in the graph

[Link] x Ψ1 (x) P

1 0 0 0

2 a/4 2/a
√2⁄𝑎

3 a/2 0 0

4 3a/4 2/a
- √2⁄𝑎

5 a 0 0
Case III: - when n = 3: second excited state

Then we have

2 3𝜋
𝜓2 (𝑥) = √𝑎 sin 𝑥 (1)
𝑎

9 ℎ2
𝐸2 = (2)
8𝑚𝑎2

2 3𝜋
𝑃 = 𝑎 𝑠𝑖𝑛2 ( 𝑎 𝑥) (3)

For different values of x the values of wave function, probability densities can be obtained and
recorded in the table 3 and their behaviour plotted in the graph.

[Link] x Ψ1 (x) P
1 0 0 0
2 a/6 2/a
2
√
𝑎

3 a/3 0 0
4 a/2 2 2/a
--√
𝑎

5 2a/3 0 0
6 5a/6 2/a
2
√
𝑎

7 a 0 0
Problems

1. Calculate the kinetic energy of electron of wavelength 18 nm? Ans: 0.0046 eV

Solution: Given λ = 18 nm = 18 x 10-9m, h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg

ℎ2 (6.62 × 10−34 )2 6.62 × 6.62 × 10−19

𝐸= = =
2𝑚𝜆2 2 × 9.11 × 10−31 × (18 × 10−9 )2 5903

𝐽 7.424×10−22
= 7.424 × 10−22 𝑒 = = 4.63 × 10−3 = 4.63 𝑚𝑒𝑉
1.602×10−19

Kinetic energy of electron = 𝟒. 𝟔𝟑 𝒎𝒆𝑽

2. Calculate the de Broglie wavelength of an electron moving with one tenth part of the
velocity of light?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg, ve = c/10 = 3 x 108/10 =3 x 107 m/s.

ℎ 6.62 ×10−34
𝜆= = = 0.242 × 10−10 𝑚 = 0.242 Å
𝑚𝑣 9.11×10−31 ×3 ×107

The de Broglie wavelength of electron = 0.242 Å

3. Calculate the de Broglie wavelength associated with an electron whose speed is with
0.001 part of the velocity of light?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg, ve = c x 0.001 = 3 x 108 x 0.001 =3
x 105 m/s.

ℎ 6.62 ×10−34
𝜆= 𝑚𝑣
= 9.11×10−31 ×3 ×105
= 0.242 × 10−8 𝑚 = 0.00242 Å

The de Broglie wavelength of electron = 𝟎. 𝟎𝟎𝟐𝟒𝟐 Å

4. Find the kinetic energy of a neutron in eV for which the de Broglie wavelength is 1 Å ?
Given mass of the neutron is 1.674 x 10-27kg.

Solution: Given λ = 1Å= 10-10m, h = 6.62 x 10-34 Js, mn = 1.674 x 10-27 kg

ℎ2 (6.62 × 10−34 )2 6.62 × 6.62 × 10−21

𝐸= = =
2𝑚𝜆2 2 × 1.674 × 10−27 × (10−10 )2 3.348

𝐽 13.09 × 10−21
= 13.09 × 10−21 = = 8.17 × 10−2 = 0. 0817 𝑒𝑉
𝑒 1.602 × 10−19

Kinetic energy of electron = 𝟎. 𝟎𝟖𝟏𝟕 𝒆𝑽

5. Calculate wavelength associated with an electron of energy 1.5 eV?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝐸 = 1.5 𝑒𝑉 = 1.5 × 1.602 × 10−19 𝑉 = 2.403 × 10−19 𝑉

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = 6.617×10−25 = 1 × 10−9 𝑚 = 0.1 Å
𝑝 √2𝑚𝐸 √2×9.11×10−31 ×2.403×10−19

The wave length of electron =𝟎. 𝟏 Å

6. Calculate the wavelength associated with an electron raised through a potential difference
of 2 kV?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝐸 = 2 𝑒𝑉 = 2 × 1.602 × 10−19 𝑉 = 3.204 × 10−19 𝑉

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = = 0.866 × 10−9 𝑚 = 0.0866 Å
𝑝 √2𝑚𝐸 √2×9.11×10−31 ×3.204×10−19 7.64×10−25

The wave length of electron =𝟎. 𝟎𝟖𝟔𝟔 Å

7. Calculate the wavelength associated with an electron having K.E. 100 eV?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝐸 = 100 𝑒𝑉 = 100 × 1.602 × 10−19 𝑉 = 160.2 × 10−19 𝑉

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = 5.402×10−24 = 1.225 × 10−10 𝑚 = 0.1 Å
𝑝 √2𝑚𝐸 √2×9.11×10−31 ×160.2×10−19

The wave length of electron = 𝟏. 𝟐𝟐𝟓 Å

8. Calculate the de Broglie wavelength of a neutron moving with K.E. 54 eV? Given the
mass of neutron 1.675x10-27kg.

Solution: Given h = 6.62 x 10-34 Js, me = 1.675 x 10-27 kg,

𝐸 = 54 𝑒𝑉 = 54 × 1.602 × 10−19 𝑉 = 86.508 × 10−19 𝑉

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = 1.702×10−22 = 3.89 × 10−12 𝑚 = 0. 0389 Å
𝑝 √2𝑚𝐸 √2×1.675×10−27 ×86.508×10−19

The wave length of electron =𝟎. 𝟎𝟑𝟖𝟗 Å

9. Calculate the de Broglie wavelength of bullet of mass 5 kg travelling with velocity of 200
m/s?

Solution: Given h = 6.62 x 10-34 Js, m = 5 kg V = 200 m/s

 ℎ 6.62 × 10−34 6.62 × 10−34
𝜆= = = = 6.62 × 10−37 𝑚
𝑝 5 × 200 1000

The de Broglie Wavelength of ball = 𝟔. 𝟔𝟐 × 𝟏𝟎−𝟑𝟕 𝒎

10. Find the de Broglie wavelength of an electron having K.E. 1.6 x10-19 J?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝐸 = 16 × 10−19 𝐽

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = = 1.227 × 10−10 𝑚 = 1.227 Å
𝑝 √2𝑚𝐸 √2×9.11×10−31 ×16×10−19 5.402×10−24

The wave length of electron = 𝟏. 𝟐𝟐𝟕 Å

11. Calculate the wavelength of the wave associated with an electron of K.E. 1 eV?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝐸 = 1 × 1.6 × 10−19 𝐽

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = = 5.402×10−24 = 1.227 × 10−10 𝑚 = 1.227 Å
𝑝 √2𝑚𝐸 √2×9.11×10−31 ×16×10−19

The wave length of electron = 𝟏. 𝟐𝟐𝟕 Å

12. A dust particle drops under gravity. Due to the frictional resistance by air molecules its
acceleration gets cancelled and it moves down with velocity of 2 cm/s. calculate its de
Broglie wavelength if its mass is 0.5x10-6kg ?

Solution: Given h = 6.62 x 10-34 Js, m = 0.5 x 10-6 kg, v= 2𝑐𝑚 = 2 × 10−2m/s

ℎ ℎ 6.62 ×10−34 6.62 ×10−34

𝜆= = = 0.5 ×10−6 ×2×10−2 = = 6.62 × 10−27 𝑚
𝑝 𝑚𝑣 10−7

The wave length of electron =6.62 × 10−27 𝑚

13. Estimate the potential difference through which an electron is needed to be accelerated
that its de Broglie wavelength becomes equal to 20 Å?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg,

𝜆 = 20Å = 20 × 10−10 𝑚

ℎ ℎ2 (6.62×10−34 )2
𝜆= ⇒ 𝑉 = 2𝑚𝑒𝜆2 = = 0.375 𝑉
√2𝑚𝑒𝑉 2×9.11×10−31 ×1.602×10−19 ×(20×10−10 )2

The required accelerating voltage is 0.375 V

14. Compare the momentum, the total energy and K.E. of an electron with a de Broglie
wavelength of 4Å, with that of photon with the same wavelength?

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg, 𝜆 = 4 Å = 4 × 10−10 𝑚, c =

3x 108 m/s

ℎ2 (6.62×10−34 )2 43.8244×10−17
𝐾. 𝐸. = 𝐸𝐾.𝐸. = 2𝑚𝜆2 = = = 0.15 × 10−17 𝐽,
2×9.11×10−31 × (4×10−10 )2 291.52

Rest mass energy of electron𝐸0 = 𝑚0 𝑐 2 = 9.11 × 10−31 × (3 × 108 )2 = 8.19910−14 𝐽

Total energy of electron = K.E. + Rest mass energy of electron = 0.15 × 10−17 𝐽 +
8.199 × 10−14 𝐽 = 8.199 × 10−14 𝐽

ℎ𝑐
Tℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑝ℎ𝑜𝑡𝑜𝑛 𝑖𝑠 𝑡ℎ𝑒 𝑜𝑛𝑙𝑦 𝐾. 𝐸. , 𝐻𝑒𝑛𝑐𝑒 𝐸𝑝ℎ = ℎ𝜈 = =
𝜆
6.62×10−34 ×3×108
= 4.965 × 10−16 𝐽
4 ×10−10

𝐸𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑒 8.199 × 10−14

𝑐𝑜𝑚𝑝𝑎𝑟𝑖𝑠𝑜𝑖𝑛 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 = = = 165
𝐸𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑝ℎ 4.965 × 10−16

𝐸𝐾.𝐸. 𝑜𝑓 𝑒 0.15×10−17
𝑐𝑜𝑚𝑝𝑎𝑟𝑖𝑠𝑜𝑖𝑛 𝑜𝑓 𝐾. 𝐸. 𝑒𝑛𝑒𝑟𝑔𝑦 = 𝐸 = = 0.003
𝐾.𝐸. 𝑜𝑓 𝑝ℎ 4.965×10−16

15. Compare the energy of photon with that of electron when both are associated with a
wavelength 0.2 nm.

Solution: Given h = 6.62 x 10-34 Js, me = 9.11 x 10-31 kg, 𝜆 = 4 Å = 4 × 10−10 𝑚, c =

3x 108 m/s

ℎ2 (6.62×10−34 )2 43.8244×10−17
𝐾. 𝐸. = 𝐸𝐾.𝐸. = 2𝑚𝜆2 = = = 0.600 × 10−17 𝐽,
2×9.11×10−31 × (2×10−10 )2 72.88

Rest mass energy of electron𝐸0 = 𝑚0 𝑐 2 = 9.11 × 10−31 × (3 × 108 )2 = 8.199 ×

10−14 𝐽

Total energy of electron = K.E. + Rest mass energy of electron = 0.15 × 10−17 𝐽 +
8.199 × 10−14 𝐽 = 8.199 × 10−14 𝐽

ℎ𝑐
Tℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑝ℎ𝑜𝑡𝑜𝑛 𝑖𝑠 𝑡ℎ𝑒 𝑜𝑛𝑙𝑦 𝐾. 𝐸. , 𝐻𝑒𝑛𝑐𝑒 𝐸𝑝ℎ = ℎ𝜈 = =
𝜆
6.62×10−34 ×3×108
= 9.93 × 10−16 𝐽
2×10−10

𝑬𝑻𝒐𝒕𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒆 𝟖. 𝟏𝟗𝟗 × 𝟏𝟎−𝟏𝟒

𝒄𝒐𝒎𝒑𝒂𝒓𝒊𝒔𝒐𝒊𝒏 𝒐𝒇 𝒕𝒐𝒕𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 = = = 𝟖𝟐. 𝟓𝟔
𝑬𝑻𝒐𝒕𝒂𝒍 𝒆𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒑𝒉 𝟗. 𝟗𝟑 × 𝟏𝟎−𝟏𝟔

16. A particle of mass 0.65 MeV/c2 has a free energy 120 eV. Find its de Broglie wavelength?
 0.65 × 106 ×1.602 × 10−19 1.041×10−29
Solution: Given mass of particle 𝑚 = = = 1.157 ×
(3 × 108 )2 9
−30
10 𝑘𝑔

Free energy of the 𝐸 = 120 × 1.602 × 10−19 = 1.92 × 10−17 𝐽

ℎ 6.62 × 10−34 6.62 × 10−34

𝜆= = = = 1 × 10−10 𝑚 = 1Å
√2𝑚𝐸 6.67×10−24
√2 ×1.157×10−30 ×1.92 ×10−17

𝒅𝒆 𝑩𝒓𝒐𝒈𝒍𝒊𝒆 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉 𝝀 = 𝟏 Å

17. What is the de Broglie wavelength of proton whose energy is 3 eV? Given that mass of
proton is 1.67x10-27kg.

Solution: Given 𝐸 = 3 × 1.602 × 10−19 = 4.806 × 10−19 𝐽, 𝑚𝑝 = 1.67 × 10−27 , ℎ =

6.62 × 10−34 𝐽 − 𝑠

ℎ 6.62 × 10−34 6.62 × 10−34

𝜆= = = = 1.65 × 10−11 𝑚 = 0.165Å
√2𝑚𝐸 4.0065×10−23
√2×1.67 × 10−27 ×4.806×10−19

18. Show that the de Broglie wavelength of an accelerated electron is found to be equal to
12.26
𝜆= Å
√𝑉

ℎ
Solution: Let us consider 𝜆 =
√2𝑚𝐸

In the above equation substitute the values of h, me, and E = eV =1.602 x 10-19x 1 = 1.602 x
10-19J

6.62 × 10−34 6.62 × 10−34 1.225×10−9

Then we get ℎ = = 5.40×10−25 =
√2×9.11 × 10−31 ×1.602×10−19 ×𝑉 √𝑉 √𝑉

12.25×10−10 12.25
= 𝑚= Å
√𝑉 √𝑉

19. Calculate the de Broglie wavelength of particle of mass 0.65 MeV/c2 and of K.E. 80 eV?
Where c is the velocity of light.

Solution: Given mass of particle

0.65 × 106 ×1.602 × 10−19 1.041×10−29

𝑚= = = 1.157 × 10−30 𝑘𝑔
(3 × 108 )2 9

Free energy of the 𝐸 = 80 × 1.602 × 10−19 = 1.28 × 10−17 𝐽

ℎ 6.62 × 10−34 6.62 × 10−34

𝜆= = = = 1.217 × 10−10 𝑚 = 1.217 Å
√2𝑚𝐸 5.44×10−24
√2 ×1.157×10−30 ×1.28 ×10−17
𝒅𝒆 𝑩𝒓𝒐𝒈𝒍𝒊𝒆 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉 𝝀 = 𝟏. 𝟐𝟏𝟕 Å

20. The velocity of an electron of a hydrogen atom in the ground state is 2.19 x 106 m/s.
calculate the wavelength of the de Broglie waves associated with it’s motion?

Solution: Given me = 9.11 x 10-31kg, h = 6.62 x 10-34Js, v = 2.19 x 106 m/s

ℎ 6.62 × 10−34
𝜆= = = 0.332 × 10−9 𝑚 = 3.32 × 10−10 𝑚
𝑚𝑣 9.11 × 10−31 × 2.19 × 106

𝜆 = 𝟑. 𝟑𝟐 Å

𝒅𝒆 𝑩𝒓𝒐𝒈𝒍𝒊𝒆 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏 𝝀 = 𝟑. 𝟑𝟐 Å

21. The position and momentum of an electron with energy 1 keV are simultaneously
determined. If its position is located within 1 Å. What is the minimum percentage of
uncertainty in its momentum?

Solution: Given 𝐸 = 1 × 103 × 1.602 × 10−19 = 1.602 × 10−16 𝐽,

∆𝑥 = 1Å = 10−10 𝑚, ℎ = 6.62 × 10−34 𝐽𝑠, 𝑚 = 9.11 × 10−31 𝑘𝑔

Momentum of electron 𝑝 = √2𝑚𝐸 = √2 × 9.11 × 10−31 × 1.602 × 10−16 = 1.71 ×

10−23 𝑁𝑠

ℎ ℎ 6.62 × 10−34
𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝑥. ∆𝑝 = ⇒ ∆𝑝 = =
4𝜋 4𝜋∆𝑥 4 × 3.142 × 10−10
6.62
= 12.568 × 10−24 = 0.527 × 10−24 𝑁𝑠

∆𝑝 5.27×10−23
Minimum % of uncertainty in momentum = × 100 = 1.71×10−23 × 100 = 3.24%
𝑝

22. In a measurement that involved a minimum uncertainty of 0.003% the speed of electron
was found to be 800 m/s. calculate the corresponding uncertainty involved in determining
its position?

Solution: Given v = 800 m/s, mass of electgron m = 9.11 × 10−31 kg

uncertainty involved in the measure𝑚𝑒𝑛𝑡 𝑜𝑓 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑖𝑠 0.003%

0.003
ℎ𝑒𝑛𝑐𝑒 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 𝑖𝑛 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 ∆𝑣 = 800 ×
100
𝑚
= 0.024 𝑢𝑛𝑐𝑒𝑟𝑡𝑖𝑎𝑛𝑡𝑦 𝑖𝑛 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 = ∆𝑝 = 𝑚𝑣
𝑠
23. The velocity of an electron of a hydrogen atom in the ground state is 2.19 x 106 m/s.
calculate the wavelength of the de Broglie waves associated with it’s motion?

Solution: Given me = 9.11 x 10-31kg, h = 6.62 x 10-34Js, v = 2.19 x 106 m/s

ℎ 6.62 × 10−34
𝜆= = = 0.332 × 10−9 𝑚 = 3.32 × 10−10 𝑚 = 𝟑. 𝟑𝟐 Å
𝑚𝑣 9.11 × 10 −31 × 2.19 × 106

𝒅𝒆 𝑩𝒓𝒐𝒈𝒍𝒊𝒆 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏 𝝀 = 𝟑. 𝟑𝟐 Å

24. The position and momentum of an electron with energy 1 keV are simultaneously
determined. If its position is located within 1 Å. What is the minimum percentage of
uncertainty in its momentum?

Solution: Given 𝐸 = 1 × 103 × 1.602 × 10−19 = 1.602 × 10−16 𝐽,

∆𝑥 = 1Å = 10−10 𝑚, ℎ = 6.62 × 10−34 𝐽𝑠, 𝑚 = 9.11 × 10−31 𝑘𝑔

Momentum of electron 𝑝 = √2𝑚𝐸 = √2 × 9.11 × 10−31 × 1.602 × 10−16 = 1.71 ×

10−23 𝑁𝑠

ℎ ℎ 6.62 × 10−34 6.62

𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝑥. ∆𝑝 = ⇒ ∆𝑝 = = = × 10−24
4𝜋 4𝜋∆𝑥 4 × 3.142 × 10−10 12.568

= 0.527 × 10−24 𝑁𝑠

∆𝑝 5.27×10−23
Minimum % of uncertainty in momentum = × 100 = 1.71×10−23 × 100 = 3.24%
𝑝

25. In a measurement that involved a minimum uncertainty of 0.003% the speed of electron
was found to be 800 m/s. calculate the corresponding uncertainty involved in determining
its position?

Solution: Given v = 800 m/s, mass of electgron m = 9.11 × 10−31 kg

uncertainty involved in the measure𝑚𝑒𝑛𝑡 𝑜𝑓 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑖𝑠 0.003%

0.003
ℎ𝑒𝑛𝑐𝑒 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 𝑖𝑛 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 ∆𝑣 = 800 ×
100
𝑚
= 0.024 𝑢𝑛𝑐𝑒𝑟𝑡𝑖𝑎𝑛𝑡𝑦 𝑖𝑛 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 = ∆𝑝 = 𝑚𝑣
𝑠

𝑢𝑛𝑐𝑒𝑟𝑡𝑖𝑎𝑛𝑡𝑦 𝑖𝑛 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 = ∆𝑝 = 𝑚∆𝑣 = 9.11 × 10−31 × 0.024 = 2.18 × 10−32 𝑁𝑠

ℎ ℎ 6.62 × 10−34
𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝑥. ∆𝑝 = ⇒ ∆𝑥 = = = 2.4 × 10−3 𝑚
4𝜋 4𝜋∆𝑝 4 × 3.142 × 2.18 × 10−32
Minimum uncertainty involved in the position of electron is 𝟐. 𝟒 × 𝟏𝟎−𝟑 𝒎

26. With the right choice of measuring instrument and source of illumination for the
measurement of speed of electron in an atom, and assuming no human error in it, the
maximum uncertainty in the value of speed that is going to be obtained is estimated to be
2x104 m/s. based upon the same, estimate the minimum width about which electron stays
confined in the atom.

Solution: Given ∆𝑣 = 2x104 m/s, h = 6.62x 10-34Js, m = 9.11x 10-31kg,

ℎ ℎ ℎ
𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝑥. ∆𝑝 = ⇒ ∆𝑥 = =
4𝜋 4𝜋∆𝑝 4𝜋𝑚∆𝑣

6.62 × 10−34
= 4×3.142×9.11 ×10−31 ×2×104 = 2.89 × 10−9 𝑚

The minimum width the electron confined in the atom = 2.89x10-9m

27. A spectral line of wavelength 5461Å has a width of 10-4 m. evaluate the minimum time
spent by the electrons in the excitation and de-excitation process.

Solution: Given 𝜆 = 5461Å = 5461 × 10−10 𝑚, ∆𝜆 = 10−4 𝑚

ℎ ℎ ℎ𝑐 ℎ𝑐
𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝐸. ∆𝑡 = 4𝜋 ⇒ ∆𝑡 = − −(1) 𝐸 = ℎ𝜈 = ⇒ ∆𝐸 = − 𝜆2 ∆𝜆 − −(2)
4𝜋∆𝐸 𝜆

ℎ 𝜆2
Substitute equation 2 in 1 then we get ∆𝑡 = ℎ𝑐 ⇒ ∆𝑡 = (neglecting negative
4𝜋 2 ∆𝜆 4𝜋𝑐∆𝜆
𝜆
sign)

𝜆2 (5461×10−10 )2
∆𝑡 = = = 7.91 × 10−19 𝑠
4𝜋𝑐∆𝜆 4×3.142×3×108 ×10−4

The minimum time spent ∆𝒕 = 𝟕. 𝟗𝟏 × 𝟏𝟎−𝟏𝟗 𝒔

28. On the basis of the uncertainty principle estimate the minimum energy of an electron that
is confined in cubic cavity of volume 50x50x50 Å3 .

Solution: Given∆𝑥 = ∆𝑦 = ∆𝑧 = 𝑎 = 50Å = 50 × 10−10 𝑚,

ℎ ℎ ℎ ℎ
We know that ∆𝑥. ∆𝑝 = 4𝜋 ⇒ ∆𝑝𝑥 = , ∆𝑝𝑦 = , ∆𝑝𝑧 = − −(1)
4𝜋∆𝑥 4𝜋∆𝑦 4𝜋∆𝑧

𝑝2 1 2 2 2
1 ℎ 2 ℎ 2 ℎ 2
∆𝐸 = = (𝑝 + 𝑝𝑦 + 𝑝𝑧 ) = (( ) + ( ) + ( ) )
2𝑚 2𝑚 𝑥 2𝑚 4𝜋∆𝑥 4𝜋∆𝑦 4𝜋∆𝑧

3 ℎ2
After simplifying the above equation leads to ∆𝐸 = − − − (2)
32𝜋 2 𝑚𝑎2

Substituting the constants and given quantities and the given quantities then we get
 3 × (6.62 × 10−34 )2 131.48 × 10−68
∆𝐸 = =
32 × (3.142)2 × 9.11 × 10−31 (50 × 10−10 )2 7.2 × 10−45

= 1.826 × 10−22 𝐽 = 1.14 𝑚𝑒𝑉

𝐓𝐡𝐞 𝐦𝐧𝐢𝐦𝐮𝐦 𝐞𝐧𝐞𝐫𝐠𝐲 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧 𝐢𝐧 𝐜𝐮𝐛𝐢𝐜 𝐜𝐚𝐯𝐢𝐭𝐲 ∆𝑬 = 𝟏. 𝟖𝟐𝟔 × 𝟏𝟎−𝟐𝟐 𝑱

= 𝟏. 𝟏𝟒 𝒎𝒆𝑽

29. An electron is bound in an one dimensional potential well of width 1 Å but of infinite
wall high. Find its energy values in the ground state, and also in the first two excited state.

Solution: Given potential width a = 1Å= 1x 10-10m, h = 6.62 x 10-34Js, m= 9.11x 10-31kg,

n = 1, n = 2, and n = 3.

𝑛2 ℎ 2 12 ℎ2 (6.62 ×10−34 )2 10−17 𝐽

𝐸𝑛 = ⇒ 𝐸0 = = 8 ×9.11×10−31 ×(10−10 )2 = 0.601 × 10−17 𝐽 = 0.601 ×
8𝑚𝑎2 8𝑚𝑎2 𝑒

= 0.0375 𝑒𝑉 = 37.5 meV, 𝑬𝟏 = 𝟐𝟐 𝑬𝟎 = 𝟒 × 𝟑𝟕. 𝟓 = 𝟏𝟓𝟎 𝒎𝒆𝑽, 𝑬𝟐 = 𝟑𝟐 𝑬𝟎 = 𝟗 ×

𝟑𝟕. 𝟓 = 𝟑𝟑𝟕. 𝟓 𝒎𝒆𝑽

30. An electron is confined to move between two rigid walls separated by 20 Å. Find the de
Broglie wavelength representing the first 3 allowed energy states of the electron and
corresponding energies?

Solution: Given a = 20 Å = 20 x 10-10m, n = 1, 2, and 3

ℎ ℎ 𝑛2 ℎ 2
We know that 𝜆 = = − −(1) 𝐸 = − − − (2) substitute equation 2 in 1 then
𝑝 √2𝑚𝐸 8𝑚𝑎2
we get

ℎ ℎ 𝑎
𝜆= = 2 2
⇒ 𝑎𝑓𝑡𝑒𝑟 𝑠𝑖𝑚𝑝𝑙𝑖𝑓𝑖𝑐𝑎𝑡𝑜𝑖𝑛 𝑤𝑒 𝑔𝑒𝑡 𝜆 = − −(3)
𝑝 2𝑛
√2𝑚 𝑛 ℎ 2
8𝑚𝑎

2𝑎
(i) for n = 1, de broglie wavelength of electron in the ground state 𝜆0 = =
𝑛
2×20 × 10−10
= 40 × 10−10 = 40Å
1
(ii) for n =
2𝑎
2, de broglie wavelength of electron in the first excited state 𝜆0 = =
𝑛
2×20 × 10−10
= 20 × 10−10 = 20Å
2

2𝑎
31. for n = 3, de broglie wavelength of electron in the second excited state 𝜆0 = =
3
2×20 × 10−10
= 13.3 × 10−10 = 13.3 Å
3
32. The inherent uncertainty in measurement of time spent by iridium 191 nuclei in the excited
state is found to be 1.4x10-10 s. Estimate the uncertainty that results in its energy in the
excited state.
Solution: Given ∆𝑡 = 1.4 × 10−10 𝑠, ℎ = 6.62 × 10−34 𝐽𝑠

ℎ ℎ 6.62 × 10−34
𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 ∆𝐸. ∆𝑡 = ⇒ ∆𝐸 = =
4𝜋 4𝜋∆𝑡 4 × 3.142 × 1.4 × 10−10

3.76 × 10−25 𝐽
= 3.76 × 10−25 𝐽 =
𝑒
3.76×10−25 𝐽
= = 2.35 × 10−6 = 2.35 𝜇𝑒𝑉
1.602×10−19

33. In a simultaneous measurement of position and velocity of an electron moving with a

speed of 6x105 m/s. calculate the highest accuracy with which its position could be
determined if the inherent error in the measurement of its velocity is 0.001% for the speed
stated above.

Solution: Given 𝑣 = 6 x105 m/s, h = 6.62x 10-34Js, m = 9.11x 10-31kg, the inherent error in the
velocity measurement is 0.001%, ∆𝑣 = 6 x105 x 0.001/100 m/s = 6 x105 x10-5 = 6 m/s

ℎ ℎ ℎ 6.62 × 10−34
𝑤𝑒 𝑘𝑛𝑤 𝑡ℎ𝑎𝑡 ∆𝑥. ∆𝑝 = 4𝜋 ⇒ ∆𝑥 = = 4𝜋𝑚∆𝑣 = 4×3.142×9.11 ×10−31 ×6 = 9.64 × 10−6 𝑚
4𝜋∆𝑝

The minimum width the electron confined in the atom = 2.89x10-6m.

34. A quantum particle confined to one dimensional box of width ‘a’ is in its first excited state.
What is the probability of finding the particle over an interval of a/2 marked symmetrically
at the centre of the box.

Solution: Given width of one dimensional box = a, for first excited state n = 2, the wave
function of the particle in one dimensional box is given by

2 𝑛𝜋
𝜓𝑛 (𝑥) = √𝑎 sin ( 𝑎 𝑥) (1)

35.

x=a/2 is the middle of the width of the box and the two points symmetrically situated about
this point is x1 = a/4 and x2 =3a/4 which are the limits of integration

The wave function of the particle in the first excited state for n=2, is given by

2 2𝜋
𝜓1 (𝑥) = √𝑎 sin ( 𝑎 𝑥 ) (2)
The probability of particle finding within the interval of a/2 and 3a/4 which are symmetrically
situated in the first excited state is given by

2
3𝑎/4 2 3𝑎/4 2 2𝜋 2 3𝑎/4 2𝜋 2
𝑃= ∫𝑎/2 ⌊𝜓1 (𝑥)⌋ 𝑑𝑥 = ∫𝑎/2 ⌊√𝑎 sin ( 𝑎 𝑥 ) ⌋ 𝑑𝑥 = 𝑎 ∫𝑎/2 sin ( 𝑎 𝑥 ) 𝑑𝑥 =
4𝜋
2 3𝑎/4 1−cos( 𝑎 𝑥 )
∫ 𝑑𝑥
𝑎 𝑎/2 2

4𝜋
2 3𝑎/4 1 2 3𝑎/4 cos( 𝑎 𝑥 )
𝑃= ∫ 𝑑𝑥 − ∫ 𝑑𝑥
𝑎 𝑎/2 2 𝑎 𝑎/2 2

1 3𝑎/4 1 3𝑎/4 4𝜋
𝑃 = 𝑎 ∫𝑎/2 1 𝑑𝑥 − ∫𝑎/2 cos ( 𝑎 𝑥 ) 𝑑𝑥
𝑎

3𝑎
4𝜋
sin( 𝑥 ) 𝑎4
1 3𝑎/4 1 𝑎 1 3𝑎 𝑎 1 1 1
2
𝑃 = 𝑎 |𝑥|𝑎/2 − 4𝜋 ⇒ ( 4 − 4) − (sin 3𝜋 − sin 𝜋) ⇒ − 0 =
𝑎 𝑎 4𝜋 2 2
𝑎

The probability of finding the particle over an interval of a/2 marked symmetrically at
𝟏
the centre of the box is 𝑷 = 𝟐 𝒐𝒓 𝟎. 𝟓

36. A particle is moving in one dimensional potential well of infinite height and width 25 Å.
Calculate the probability of finding the particle in an interval of 5 Å at a distance of a/2,
a/3, and a. where a is the width of the well assuming that the particle is in its least energy
state.

Solution: Given one dimensional potential well of infinite height of width x = 25 Å = a

Probability will be calculated within the interval 5 Å

The points about which the probability calculated are x = a/2, a/2 and a, Given when x = a/2
= 25 Å /2 =12.5 Å, x1= 12.5 -5/2 = 12.5-2.5=10 Å

x2 =12.5 + 5/2=12.5+2.5 =15Å

The wave function of a particle in the least energy state of potential well of infinite well is
given by
 2 𝜋
𝜓0 (𝑥) = √𝑎 sin (𝑎 𝑥) for n = 1 least or ground state energy level.

The probability of finding the particle about the point x = 12.5Å, within the interval 5 Å with
lower limit of 10 Å and upper limit of 15 Å can be obtain by integrating the wave function of
particle within the limits. Hence we get
2 2𝜋
15Å 2 𝜋 2 15Å 𝜋 2 2 15Å 1−cos 𝑎 𝑥
𝑃= ∫10Å [√𝑎 sin (𝑎 𝑥)] 𝑑𝑥 = ∫ sin (𝑎 𝑥) 𝑑𝑥 = ∫ 𝑑𝑥 =
𝑎 10Å 𝑎 10Å 2
1 15Å 1 15Å 2𝜋
∫ 1 𝑑𝑥 − 𝑎 ∫10Å cos 𝑥 𝑑𝑥
𝑎 10Å 𝑎

2𝜋 15Å
1 1 sin 𝑎 𝑥 10Å 1 1 2𝜋 2𝜋
𝑃= [𝑥]15Å
10Å − 2𝜋 = (15Å − 10 Å) − 2𝜋 (sin (25Å × 15Å) − sin (25Å ×
𝑎 𝑎 25 Å
𝑎

10Å))

5 1 6𝜋 4𝜋
𝑃 = 25 − 2𝜋 (sin ( ) − sin ( )) = 0.2 − 0.159 × (−0.588 − 0.588) = 0.2 +
5 5
0.187 = 0.387

Hence the probability 𝑷 = 𝟎. 𝟑𝟖𝟕

(ii) When x= a/3

Point is x = a/3 and the interval is 5 Å

Lower (limit) point of interval = a/3 – 5Å/2 = 25Å/3 – 2.5Å = 8.33Å – 2.5Å =5.833Å

Upper (limit) point of interval = a/3 + 5Å/2 = 25Å/3 + 2.5Å = 8.33Å + 2.5Å =10.833Å

The probability of finding the particle about the point x = 8.33 Å, within the interval 5 Å with
lower limit of 5.833 Å and upper limit of 10.833 Å can be obtain by integrating the wave
function of particle within the limits. Hence we get
2 2𝜋
10.833Å 2 𝜋 2 10.833Å 𝜋 2 2 10.833Å 1−cos 𝑎 𝑥
𝑃= ∫5.833Å [√𝑎 sin (𝑎 𝑥)] 𝑑𝑥 = ∫ sin (𝑎 𝑥) 𝑑𝑥 = ∫ 𝑑𝑥 =
𝑎 5.833Å 𝑎 5.833Å 2
1 10.833Å 1 10.833Å 2𝜋
∫ 1 𝑑𝑥 − 𝑎 ∫5.833Å cos 𝑥 𝑑𝑥
𝑎 5.833Å 𝑎

2𝜋 10.833Å
1 1 sin 𝑎 𝑥 5.833Å 1 1 2𝜋
𝑃= [𝑥]10.833Å
5.833Å − 2𝜋 = (10.833Å − 5.833 Å) − 2𝜋 (sin (25Å ×
𝑎 𝑎 25 Å
𝑎
2𝜋
10.833Å) − sin (25Å × 5.833Å))

5 1
𝑃 = 25 − 2𝜋 (sin(155.99 ) + sin(83.99 )) = 0.2 − 0.159 × (0. 407 − 0.994) = 0.2 +
0.0933 = 0.2933
Hence the probability 𝑷 = 𝟎. 𝟐𝟗𝟑𝟑

Exercise problems

1. An electron has speed of 4.8x105 m/s accurate to 0.012 %. With what accuracy can be
located the position of electron?
2. A spectral line of wavelength 4000Åhas a width of 8x10-5 Å. Evaluate the minimum time
spent by the electron in the upper energy state between the excitation and de-excitation
process.
3. The velocity of an electron was measured to be 5x105 m/s with the uncertainty of 1 %.
What is the uncertainty involved in the measurement of its position.
4. An electron has a speed of 4x105 m/s accurate to 0.01%.with what fundamental accuracy
can we locate the position of electron?
5. An electron is confined to a box of length 10-8m. Calculate the minimum uncertainty in the
velocity?
6. Calculate zero point energy for an electron in a box of width 10 Å?
7. The ground state energy of an electron for an infinite well is 5.6x10-3eV. What will be the
ground state energy if the width of potential is doubled?
8. A particle is moving in one dimensional potential box of width 10 Å. Calculate the
probability of finding the particle within an interval of 1 Å at the centre of the box, when it
is in its state of least energy?
9. An electron is bound to one dimensional potential well of width 0.18 Å. Find the energy in
eV of the second excited state?
10. The first excited state energy of an electron in an infinite well is 240 eV. What will be its
ground state energy when the width of the potential well is doubled?
11. Find the probability of the particle at the centre of the box?
12. If the uncertainty in the position of a particle is equal to its de Broglie wavelength. Then
find the uncertainty in its momentum?
13. If an electron moves in one dimensional potential box of width 2 nm. And infinite height
then find the normalised constant?
14. A particle moving in one dimensional box is described by the wave function 𝜓 =
𝑥√3 𝑓𝑜𝑟 0 < 𝑥 < 1 𝑎𝑛𝑑 𝜓 = 0 𝑓𝑜𝑟 𝑒𝑙𝑠𝑒𝑤ℎ𝑒𝑟𝑒 find the probability of finding the particle
within the interval (0, 1/2)?
15. An electron is moving in a box of length and if ψ1 is wave function at x = a/4 with n = 1
and ψ2 at x = a for n = 2 then find ration of ψ2/ψ1?
16. Find the probability of the particle in a potential well of infinite height at the centre of the
box in its first excited state?
17. An electron has a speed of 100 m/s accurate to 0.05 %. Find the uncertainty in its position?
18. The uncertainty in the determination of position of an electron is h/3π. Then find the
uncertainty in its momentum?
19. The ground state energy of an electron in a one dimensional infinite potential well of width
2 Å is 16 eV. Find its energy in the third excited state?
20. The ground energy of an electron in a well of infinite well is 5.6 meV. Find the ground
energy of the electron if the potential well is doubled?