PPSC Quantum Mechanics

Quantum Mechanics (Revised Edition) 1
I-II
Quantum Mechanics
Re-visited
Ψ Notes Compiled from

David J. Griffiths | Richard L. Liboff | Nouredine Zettili
Contents
1.0 What is Quantum Mechanics?

1.1 Origin of Quantum Mechanics
1.2 Contribution of scientists
1.3 What is a Wavefunction 𝚿(𝒓, 𝒕)?
1.4 What is a Operators 𝐀 ̂?
1.5 What is a Schrödinger Wave Equation?
1.6 What is Hilbert Space 𝓗?
1.7 What is Dirac Notation?
1.8 Define Postulates of Quantum Mechanics?
1.8 What is Commutation Relation?
1.9 What is The Uncertainty Principle?
1.10 What are the Application of One Dimensional SWE?
1.11 What is Angular Momentum?
1.12 What is representation of Angular Momentum in Spherical polar co-ordinates ?
1.13 Eigenvalue and Eigenfunction of 𝑳̂𝒛 Angular Momentum?
1.14 What is Raising 𝑳̂+ and Lowering 𝑳̂− operators?
1.15 Eigenvalue 𝑳𝟐 Angular Momentum?
1.16 Matrix Representation of angular momentum?
1.17 Define the Quantum Mechanics in 3-Dimensions?
1.18 What is Many particle system?
1.19 What are Identical Particles?
1.20 What is Interchange Symmetry of Identical particles?
1.21 What are Approximation Methods for the Solution of SWE?
1.22 What is Perturbation theory?
1.23 What is Time-Independent Perturbation theory?
Time-Independent Non-degenerate Perturbation theory
Time-Independent Degenerate Perturbation theory
1.24 What is Time-Dependent Perturbation theory?
1.25 What is Variational Principle?
1.26 What is WKB Approximation?
1.27 What’s so special in Special theory of Relativity?
1.28 Differentiate between Non-Relativistics & Relativistics QM?
1.29 What is Klein Garden equation?
1.30 What is Dirac Equation?
1.0 What is Quantum Mechanics?

Quantum Mechanics is the study of the microscopic world.
Quantum Mechanics is the theory that describes the dynamics of matter at the microscopic scale.
Quantum Mechanics is the branch of physics in which the bodies whose velocity approaches the speed of light v → c.
e.g. 2 × 107 m/s is the velocity of electron approaches to speed of light 3 × 108 m/s of light.
Quantum mechanics is the founding basis of all modern physics: solid state, molecular, atomic, nuclear, and particle physics, optics,
thermodynamics, statistical mechanics, chemistry and biology
 Quantized Quantity
Quantized quantity is certain minimum amounts (or some minimum constant).
Quantized quantity is Integral multiple of certain minimum amounts (or some minimum constant).
e.g. Energy formula 𝐸 = ℎ𝑓, E is quantized quantity because E is integral multiple certain minimum amounts or Planck’s
constant ℎ = 6.63 × 10−34 𝑗𝑠
 Quantum (Quanta)
The certain minimum amount that is associated with a quantity is called the Quantum or Quanta of that quantity.
e.g. Light is quantized and its Quanta is called photons.
The word Quantum derives from

the Latin, meaning "how great" or
"how much"
1.1 Origin of Quantum Mechanics

 At the the end of the 19th century, many scientists believed that they had completely understand all the phenomena happening
in universe.
 But certain phenomenon—such as blackbody radiation, the photoelectric effect, atomic stability, and atomic
spectroscopy— created new problems which were not solved by Newtonian or Classical physics.(19th century physics)
 This give birth to new physics branch called Quantum Physics.
1.2 Contribution of scientists

Max Plank’s ___ The Blackbody Radiation
 In 1909 Max Plank’s introduced concept of Quantum of energy (photon) to explain -- Blackbody radiation.
 He proposed that energy of radiation (light) is Quantized and dependent of frequency as 𝐸 = ℎ𝑓 where h is the plank’s
constant of value ℎ = 6.63 10 × 10−34 𝐽 𝑠
Albert Einstein ____ The Photoelectric Effect
 In 1905 Einstein confirmed the Planck’s quantum concept.

 Einstein proposed that electromagnetic radiation (light) is quantized and exists in fixed amounts (quanta) or photons.
 The introduction of the photon concept enabled Einstein to give explanation to the photoelectric problem, by Hertz in 1887.
Niels Bohr ___ The model of Hydrogen atom
 Bohr proposed that atoms can found only in discrete states of energy.
 The emission or Absorption of radiation (or light) by atoms, takes place only in discrete amounts of 𝐸 = ℎ𝑓.
Arther Holy Compton ____ Compton’s effect
 By scattering X-rays with electrons, He confirmed that the (X-ray) photons behave like particles.
 Loss in photon energy = gain in electron energy
de Broglie ___ Matter is a wave and wave is a matter too!
 In 1923, de Broglie proposed that Matter waves.

ℎ ℎ
 He showed that wave nature of matter by relation___ 𝜆 = =
𝑚𝑣 𝑝
 In 1927 by Davisson and Germer proved de Broglie hypothesis.
Heisenberg___ The Uncertainty principle ( One thing at a Time!)

ℏ
 In 1925 , Heisenberg proposed that it is impossible to determine the exact position and momentum at same time. Δ𝑝𝑥 . Δ𝑥 ≥
2
 There is always be the Uncertainty (but multiple) of ℏ. It is open challenge and basis of Quantum Mechanics.
 He say that Quantum mechanics is a completely indeterministic theory, no one know the future state of particle. E.g three
wings of rotating fans.
 He formulated the Matrix Quantum Mechanics in which Eigen values are represented in matrices.
Erwin Schrödinger___ The Schrodinger Wave Equation of Particle (SWE)
 In Quantum Mechanics Schrodinger Wave Equation play a same role like Newton’s Second Law: 𝐹 = 𝑚𝑎
 In 1926, Schrodinger describe the dynamics of microscopic particles with a wave equation called Schrodinger Wave
Equation.
 Schrodinger Wave Equation is 2nd order differential equation i.e
𝐻Ψ = 𝐸Ψ
2 2
ℏ 𝜕 Ψ 𝜕Ψ
− + 𝑉(𝑟) = 𝑖ℎ
2𝑚 𝜕 2 𝑥 𝜕𝑡
Where H is Hamilton Operator or Total Energy Operator, Ψ is the wavefunction , E is the Energy Operator, V(r) is potential and
ℎ
ℏ is modified formed of Planck’s constant .i.e ℏ = = 1.054573 × 10−34 𝐽𝑠
2
 The solution of SWE is a Wavefunction Ψ(𝑟, 𝑡). A wavefunction completely describe the de-Broglie waves in space with
respect to time.
 Schrödinger give the wave formulation of Quantum Mechanics
Paul Dirac___ An easy <Bra|Ket> Notation of wavefunction 𝜳 and Relativistic approaches
 Dirac then suggested a more general formulation of quantum mechanics using two state vectors i.e Bras and Ket sVectors
 The Kets notation of wavefunction Ψ is |Ψ > while Bra notation of Ψ is < Ψ|.
Where Kets |Ψ >= ∫ Ψ𝑑𝑥 and Bras < Ψ| = ∫ Ψ ∗ 𝑑𝑥
1.31 What is a Wavefunction 𝚿(𝒓, 𝒕)?
A wavefunction contain all the information of the particles at any instant of time.
A wave function is the variable quantity which explain de-Broglie wave.
It is represented by Greek letter Psi Ψ(𝑟, 𝑡). It is function of space-coordinate and time.
𝛹(𝑟, 𝑡) = 𝛹(𝑟)𝑓(𝑡)
Properties of wavefunction:
Wave functions cannot be
localized in Quantum Mechanics
1. It is single value and non-negative function.
2. It is the solution of Schrödinger wave equation.
3. It is finite & continuous everywhere.
4. Born’s Statistical Interpretation or Probability Density:
The probability of finding the particle at point x at time t is given by taking square of absolute value of
wavefuction.|Ψ|2 .
5. |Ψ|2 is equal to intensity of matter
Probability = |Ψ|2 𝑑𝑥 . waves. This intensity is directly
proportional to probability of particle
at point x.
Where Ψ = 𝑎 + 𝑖𝑏 , Ψ ∗ = 𝑎 − 𝑖𝑏 and |Ψ|2 is probability density.
6. The magnitude of wavefuction is said to be large in region where probability of finding particle is large and vice versa.
Normalization or Square integrable: (Condition of Normalization)
If we consider whole space (+∞, −∞) the probability of finding particle become maximum or unity. It is given as by the
condition
+∞ +∞
∫ |Ψ|2 𝑑𝑥 = ∫ Ψ Ψ ∗ = 1
−∞ −∞
Orthognality: (Condition of orthognality)

The probability of finding particle for Minimum or Zero condition is given by, . It is given as by the condition as,
+∞ +∞ Probability is either be 1 or 0
∫ |Ψ|2 𝑑𝑥 = ∫ Ψ Ψ ∗ = 0 1 indicates High probability
−∞ −∞ 0 indicates Low probability
Orthonormalization: (Condition of Normalization + othognalization)

This condition is represented by Knocker delta fuction 𝛿𝑚𝑛 as
+∞ +∞
∫ |Ψ|2 𝑑𝑥 = ∫ Ψ Ψ ∗ = 𝛿𝑚𝑛
−∞ −∞
Where 𝛿𝑚𝑛 is Knocker delta function given as,
0, 𝑤ℎ𝑒𝑛 𝑚 ≠ 𝑛
𝛿𝑚𝑛 = {
1, 𝑤ℎ𝑒𝑛 𝑚 = 𝑛
Q Why normalization is necessary?

As wave mechanics deals with Normalized functions, any wave function which is not normalized has no physical
meaning in quantum mechanics. And Schrödinger Wave equation cannot be solved without it.
̂?
1.32 What is a Operators 𝐀
An operator 𝐴̂ is a mathematical rule when applied on wavefunction Ψ transform it to another wavefunction Ψ́ (Eigenfuction).
An operator operates on wavefunction and make it something else except for identity 1.
𝐴̂Ψ = 𝑎Ψ ́ ____Eigenvalue Equation Eigen Value Equation is

where 𝑨̂ is the operator, a is the Eigen value and Ψ ́is the Eigen function 𝐴̂Ψ = 𝑎Ψ
Operator (Function)=Eigen Value(Eigen
function)
Q. What is linear operator?

An operator 𝑨̂ is said to be linear if it obeys the distributive law and, like all operators, it commutes with constants.
e.g Hamiltonian Operator, Energy operator and all below explained operators.
𝐴̂(𝑎𝜓1 + 𝑎𝑏) = 𝑎𝐴̂𝜓1 + 𝑎𝐴̂𝑏
Example of Operator:
 Inverse Operator 𝑨̂ −𝟏 : When applied on wavefunction changes into the Identity operator 𝐼. ̂
𝐴̂ 𝐴̂ = 𝐴̂𝐴̂ = 𝐼̂
−1 −1
 Identity Operator 𝑰̂: Which leave the wavefunction unchanged

𝐼̂𝐴̂ = 𝐴̂𝐼̂ = 𝐴̂
 Unitary Operator: A operator U is said to be unitary if its inverse 𝑈 ̂ −1 is equal to its adjoint U†.
̂𝔨 = 𝑈
𝑈 ̂ −1
 Del Operator:
𝜕 𝜕 𝜕
̂= 𝑖̂
∇ + 𝑗̂ + 𝑘̂
𝜕𝑥 𝜕𝑦 𝜕𝑧
 Laplacian Operator:
𝜕2 𝜕2 𝜕2
̂2 =
∇ + +
𝜕2𝑥 𝜕2𝑦 𝜕2𝑧
 Linear Momentum Operator 𝒑 ̂: (Hermitian Operator)
𝜕 𝜕 𝜕
𝑝̂𝑥 = −𝑖ℏ ∶ 𝑝̂𝑦 = −𝑖ℏ ∶ 𝑝̂𝑧 = −𝑖ℏ ____1 Dimension
𝜕𝑥 𝜕𝑦 𝜕𝑧
̂ _____ 3 Dimension
𝑝̂ = −𝑖ℏ∇
 Energy Operator 𝑬̂ :
𝜕 Hermitian Operator A Hermitian matrix is one
𝐸̂ = 𝑖ℎ where its conjugate transpose is itself. For
𝜕𝑡
operators, the term \adjoint" is often used. A
 ̂:
Kinetic Energy Operator 𝑻 Hermitian operator is also called a self-adjoint
ℏ2 2 operator.
𝑇̂ = 𝑖 ∇ They have real Eigenvalues
2𝑚 ̂𝔨 = 𝑀
̂
𝑀
 ̂ : (Real Function)
Potential Energy Operator 𝑽
𝑉̂ = 𝑉(𝑟, 𝑡)
 ̂ : (Hermitian Operator)
Hamiltonian Operator or Total energy operator 𝑯

̂ = 𝑇̂ + 𝑉̂
𝐻
ℏ2 2
̂=−
𝐻 ∇ + 𝑉̂
2𝑚
ℏ2 𝜕 2 𝜕2 𝜕2
̂=−
𝐻 ( 2 + 2 + 2 ) + 𝑉̂
2𝑚 𝜕 𝑥 𝜕 𝑦 𝜕 𝑧
 Projection Operator 𝑷 ̂ : An operator P is said to be a projection operator if it is Hermitian and equal to its own
square.
𝑃̂ 𝔨 = 𝑃̂ ∶ 𝑃̂2 = 𝑃̂
For instance, The unit operator I is a simple example of a projection operator, since 𝐼̂𝔨 = 𝐼̂ & 𝐼̂2 = 𝐼̂
Properties of projection operators:
1. The product of two commuting projection operator is also a projection operator.
2. The sum of the two projection operator is also a projection operator
3. Two projection operator are said to orthogonal if their product is zero.
 Parity Operator or Inversion Operator 𝓟 ̂:

The space reflection about the origin of the coordinate system is called an inversion or a parity operation
A parity operator simply invert (or reflect) the wavefunction 𝜓(𝑟) through space symmetry reflection 𝜓(−𝑟).
𝒫̂ 𝜓(𝑟) = 𝒫̂ 𝜓(−𝑟) and 𝒫̂ 2 = 1 𝑜𝑟 𝒫̂ = 𝒫̂ −1

e.g Identity or unit operator is parity operator as 𝐼̂2 = 𝐼̂ ∶ 𝐼̂−1 = 𝐼̂
 Exchange Operator or Permutation Operator 𝑷 ̂ 𝒊𝒋:

 An operator when act on N-particle wavefunction 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 )interchange the ith and jth particle
only 𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 ) is known as Permutation operator.
𝑃̂𝑖𝑗 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) = 𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 ) and 𝑃̂𝑖𝑗2 = 1
 Orbital Angular Momentum Operator 𝑳̂:

𝐿̂ = 𝑟̂ × 𝑝̂ = −𝑖ℏ 𝑟̂ × ∇ ____ 3 Dimension
𝐿̂ = 𝑟̂ × 𝑝̂ = (𝑦𝑝𝑧 − 𝑧𝑝𝑧 )𝑖̂ + (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂ + (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂ __3 Dimension
𝐿̂𝑥 = (𝑦𝑝𝑧 − 𝑧𝑝𝑦 )𝑖̂
𝐿̂𝑦 = (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂
𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
 ̂ (𝒕, 𝒕𝟎 ):
Time evolution operator 𝑼
|𝜓(𝑡)⟩ = 𝑈 ̂(𝑡, 𝑡0 )|𝜓(𝑡0 )⟩
̂
Where 𝑈(𝑡, 𝑡0 ) is the unitary operator known as time evolution operator or time development operator
1.33 What is a Schrödinger Wave Equation?
In 1926, Schrodinger describe the dynamics of (microscopic) particles with a wave equation called Schrodinger Wave Equation.
In Quantum Mechanics Schrodinger Wave Equation play a same role like Newton’s Second Law
Schrodinger Wave Equation is 2nd order differential equation is given as with completely define by a solution wavefunction
Ψ(𝑟, 𝑡)
𝐻̂ Ψ = 𝐸̂ Ψ
To solve SWE we assume the separable solution of wavefunction as

Ψ(𝑥, 𝑡) = 𝜓(𝑟)𝑓(𝑡) _____(1)
𝑖𝐸𝑡
−
∴ 𝑓(𝑡) = 𝑒 ℏ ____ put in eq.(1)
In Time Independent Schrödinger Wave Equation

Solutions of the Schrödinger equation will be as, We assume Potential V in only dependent of position x
𝑖𝐸𝑡 and solution is separable.
Ψ(𝑥, 𝑡) = 𝜓(𝑥) 𝑒 − ℏ  𝑽 = 𝑽(𝒙) ∶ 𝑽 ≠ 𝑽(𝒕)
 𝛹(𝑥, 𝑡) = 𝜓(𝑟)𝑓(𝑡)
Time Independent Schrödinger Wave Equation is
The Schrödinger equation describing the dynamics of a microscopic particle of mass m in a one-dimensional time-independent
potential 𝑉(𝑥) is given by
ℏ2 𝜕2
− Ψ(x) + 𝑉(𝑥)Ψ(x) = 𝐸̂ Ψ(x) ____1 Dimension
2𝑚 𝜕2 𝑥
ℏ2
− ∇2 Ψ(r) + 𝑉(𝑟)Ψ(r) = 𝐸̂ Ψ(r) _______3 Dimension
2𝑚
Similarly, the solutions of the Schrödinger equation for time-independent potentials are stationary states.
𝑖𝐸𝑡
Ψ(𝑥, 𝑡) = 𝜓(𝑥) 𝑒 − ℏ
Time Dependent Schrödinger Wave Equation is
𝜕
̂ Ψ(𝑟, 𝑡) = 𝑖ℏ
𝐻 Ψ(r, t)
𝜕𝑡
The Linear Vector Space

A linear vector space consists of two sets of elements and two algebraic rules
 Set of vectors (𝛹, 𝜓. . ) and a set of scalars (a,b,c,,,)
 A rule for vector addition and a rule for scalar multiplication.
1.34 What is Hilbert Space 𝓗?
A complete inner product space is called Hilbert space 𝓗. It includes all limits (+∞, −∞)
Hilbert space is the infinite dimensional space which consist of set of vectors (Ψ, 𝜓. . ) and set of scalars (a,b,c,,,) satisfying the
following four properties.
1. It must be Linear Vector Space.
2. The scalar product must be positive
3. It is Separable
4. It must be complete.
The state of a system is represented in Quantum Mechanics by elements of a Hilbert space; these elements are called state
vectors |Ψ > or Wavefunction Ψ(𝑟, 𝑡).
1.35 What is Dirac Notation?

Dirac suggested a more general representation of quantum mechanics using two state vectors i.e Bras and Kets Vectors
The Kets notation of wavefunction Ψ is |Ψ > , while Bra notation of wavefunction Ψ is < Ψ|.
Kets |Ψ ≥ ∫ Ψ𝑑𝑥 & Bras < Ψ| = ∫ Ψ ∗ 𝑑𝑥
Properties of Kets, Bras and Bra-kets.

1.7 Define Postulates of Quantum Mechanics?

There are five basics postulates of quantum mechanics. They cannot be derived because they are experimentally proven. They
represent the minimal set of assumptions needed to develop the theory of quantum mechanics.
1. Postulate-1:Wavefunction or state of system 𝜳(𝒓, 𝒕):

A wave function is the variable quantity which explain de-Broglie wave. It is represented by Greek letter Psi 𝛹(𝑟, 𝑡). It is
function of space-coordinate and time.
𝛹(𝑟, 𝑡) = 𝛹(𝑟)𝑓(𝑡)
2. Postulate-2:Observable and Operator:

To every Observable A there exist a corresponding Operator ̂𝐴.
i.e Energy is observable and have corresponding Energy operator 𝐸 → 𝐸̂ , 𝑝 → 𝑝̂ , 𝐻 → 𝐻,
̂ & 𝑇 → 𝑇̂ .
Observable (A): is a physical quantity that can be measured or observed. e.g Mass, Energy, Linear momentum, Angular
momentum or umber of particles etc.
̂ ): is a mathematical rule when applied on wavefunction Ψ transform it to another wavefunction Ψ́ (eigenfuction)

Operator (𝑨
An operator operates on wavefunction and make it something else except for identity 1.
𝐴̂Ψ = 𝑎Ψ ́ ____Eigenvalue Equation
Eigen is a German word means

‘Inherent’ or ‘Characteristics’
Eigen values of Hermitian operator
are reals.
3. Postulate-3: Eigenvalues of operators or Measurements of Operator:

When operator 𝐴̂ acts on wavefunction the result is just a multiple of the original wavefunction. These special wavefunctions
are called Eigenfunction, and the multiples are called Eigenvalues 𝑎𝑛 .
Eigen value is the value of energy 𝐸𝑛 for which the Schrödinger wave equation can be solved.i.e 𝐻Ψ = 𝐸𝑛 Ψ
𝐴̂Ψ = 𝑎𝑛 Ψ ́ _____ Eigen Value Equation
Where 𝑨̂ is the operator, a is the Eigen value and Ψ ́is the Eigen function
Eigen Value Equation is
𝐴̂Ψ = 𝑎𝑛 Ψ
Operator (Function)=Eigen Value(Eigen function)
Q. What is the Eigen value of Hermitian operator?

The eigenvalues of Hermitian operators are real and Eigenfuction are orthogonal.
The eigenvalues of a symmetric matrix are real; the eigenvectors form an orthonormal basis.
The eigenvalues of an antisymmetric matrix are purely imaginary or zero.
The eigenvalues of a Hermitian matrix are real; the eigenvectors form an orthonormal basis.
The eigenvalues of a skew-Hermitian matrix are purely imaginary or zero.
The eigenvalues of a unitary matrix have absolute value equal to one.
If the eigenvalues of a square matrix are not degenerate (distinct), the corresponding eigenvectors form a basis (i.e., they form
a linearly independent set).
4. Postulate-4: Expectation value or Probabilistic outcome of measurements:

The average or mean value of operator 𝐴̂ is known as Expectation value.
<Ψ|𝐴|Ψ>̂
Expectation value of operator 𝐴̂ =
<Ψ|Ψ>
e.g Hamiltonian is the Expectation value of Energy operator 𝐸̂ =< Ψ|𝐻

̂ |Ψ >
5. Postulate-5: Time Evolution of system

The time development of the Wavefunction 𝛹(𝑟, 𝑡) of a particle at any time t is according to the time-dependent Schrödinger
equation.
To examine how quantum states evolve in time we use time-dependent Schrödinger equation.
𝜕
̂ Ψ(𝑟, 𝑡) = 𝑖ℏ
𝐻 Ψ(r, t)
𝜕𝑡
1.36 What is Commutation Relation?
Commutator or Commutation: is an operation between the two operators 𝐴̂ and 𝐵̂ . It can be written as [𝐴̂, 𝐵̂ ] and defined by
[𝐴̂, 𝐵̂ ] = 𝐴̂𝐵̂ − 𝐵̂ 𝐴̂ ___(a)
1. Two operators 𝐴̂ & 𝐵̂ are said to commute if their commutator is equal to zero
[𝐴̂, 𝐵̂ ] = 0
𝐴̂𝐵̂ − 𝐵̂ 𝐴̂ = 0 from (a)
𝐴̂𝐵̂ = 𝐵̂ 𝐴̂
̂ ̂
e.g. any operator commutes with itself, [𝐴, 𝐴] = 0, [𝑥, 𝑝̂𝑦 ] = 0
2. Two operators 𝐴̂ & 𝐵̂ are said to anti-commute if their commutator is not equal to zero.
[𝐴̂, 𝐵̂ ] ≠ 0
𝐴̂𝐵̂ − 𝐵̂ 𝐴̂ ≠ 0
𝐴̂𝐵̂ ≠ 𝐵̂ 𝐴̂
e.g. [𝐿̂𝑥 , 𝐿̂𝑥 ] = 0, [𝑥, 𝑝̂𝑥 ] = −𝑖ℏ
Important Commutation Relation:
1. Canonical commutation relations[𝑋̂, 𝑃̂ ]: The commutation relation between position 𝑋̂ and momentum 𝑃̂ .
(i) [𝑥̂, 𝑝̂𝑥 ] = −𝑖ℏ

To determine the commutation we use an arbitrary test function 𝑓(𝑥) on R.H.S
R.H.S
= [𝑥̂, 𝑝̂𝑥 ]𝑓(𝑥)
= [𝑥̂𝑝̂𝑥 − 𝑝̂𝑥 𝑥̂]𝑓(𝑥)
𝜕 𝜕
= [𝑥̂ (−𝑖ℏ ) − (−𝑖ℏ )𝑥̂] 𝑓(𝑥)
𝜕𝑥 𝜕𝑥
𝜕 𝜕
= [𝑥̂ (−𝑖ℏ ) 𝑓(𝑥) − (−𝑖ℏ )𝑥̂𝑓(𝑥) ]
𝜕𝑥 𝜕𝑥
𝜕 𝜕
= −𝑖ℏ [𝑥̂ ( ) 𝑓(𝑥) − ( )𝑥̂𝑓(𝑥) ]
𝜕𝑥 𝜕𝑥
𝜕𝑓(𝑥) 𝜕𝑓(𝑥) 𝜕𝑥̂
= −𝑖ℏ [𝑥̂ − 𝑥̂ − 𝑓(𝑥)]
𝜕𝑥 𝜕𝑥 𝜕𝑥
𝜕𝑓(𝑥) 𝜕𝑓(𝑥)
= −𝑖ℏ [𝑥̂ − 𝑥̂ − 𝑓(𝑥)]
𝜕𝑥 𝜕𝑥
= −𝑖ℏ[ −𝑓(𝑥)]
⇒ [𝑥̂, 𝑝̂𝑥 ]𝑓(𝑥) = 𝑖ℏ𝑓(𝑥) Cancelling 𝑓(𝑥)𝑜𝑛 𝑏𝑜𝑡ℎ 𝑠𝑖𝑑𝑒𝑠
Hence
[𝑥̂, 𝑝̂𝑥 ] = 𝑖ℏ
Similarly we can prove
[𝑦̂, 𝑝̂𝑦 ] = 𝑖ℏ
[𝑧̂ , 𝑝̂𝑧 ] = 𝑖ℏ
Hence
[𝑥̂, 𝑝̂𝑥 ] = [𝑦̂, 𝑝̂𝑦 ] = [𝑧̂ , 𝑝̂𝑧 ] = 𝑖ℏ Same do not commutes.
[𝑝̂𝑥 , 𝑥̂] = [𝑝̂𝑦 , 𝑦̂] = [𝑝̂𝑧 , 𝑧̂] = −𝑖ℏ
(ii) [𝑥̂, 𝑝̂𝑦 ] = 0

To determine the commutation we use an arbitrary test function 𝑓(𝑥) on R.H.S
R.H.S
= [𝑥̂, 𝑝̂𝑦 ]𝑓(𝑥)
= [𝑥̂𝑝̂𝑦 − 𝑝̂𝑦 𝑥̂]𝑓(𝑥)
𝜕 𝜕
= [𝑥̂ (−𝑖ℏ ) − (−𝑖ℏ
)𝑥̂] 𝑓(𝑥)
𝜕𝑦 𝜕𝑦
𝜕 𝜕
= [𝑥̂ (−𝑖ℏ ) 𝑓(𝑥) − (−𝑖ℏ )𝑥̂𝑓(𝑥) ]
𝜕𝑦 𝜕𝑦
𝜕 𝜕
= −𝑖ℏ [𝑥̂ ( ) 𝑓(𝑥) − ( )𝑥̂𝑓(𝑥) ]
𝜕𝑦 𝜕𝑦
𝜕𝑓(𝑥) 𝜕𝑓(𝑥) 𝜕𝑥̂
= −𝑖ℏ [𝑥̂ − 𝑥̂ − 𝑓(𝑥)]
𝜕𝑦 𝜕𝑦 𝜕𝑦
𝜕𝑓(𝑥) 𝜕𝑓(𝑥)
= −𝑖ℏ [𝑥̂ − 𝑥̂ − 0]
𝜕𝑦 𝜕𝑦
= −𝑖ℏ[ 0]
⇒ [𝑥̂, 𝑝̂𝑦 ]𝑓(𝑥) = 0
Hence
[𝑥̂, 𝑝̂𝑦 ] = 0
[𝑥̂, 𝑝̂𝑦 ] = [𝑥̂, 𝑝̂𝑧 ] = [𝑦̂, 𝑝̂𝑥 ] = [𝑦̂, 𝑝̂𝑧 ] = [𝑧̂ , 𝑝̂𝑥 ] = [𝑧̂, 𝑝̂𝑥 ] = 0 Different commutes.
2. Orbital Angular momentum commutation L:

Since we know that
𝐿̂𝑥 = (𝑦𝑝𝑧 − 𝑧𝑝𝑦 )𝑖̂ ∶ 𝐿̂𝑦 = (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂ ∶ 𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂ _
(i) [𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ℏ𝐿̂𝑧

𝑅. 𝐻. 𝑆
= [𝐿̂𝑥 , 𝐿̂𝑦 ]
= [𝑦𝑝𝑧 − 𝑧𝑝𝑦 , 𝑧𝑝𝑥 − 𝑥𝑝𝑧 ]
= [𝑦𝑝𝑧 , 𝑧𝑝𝑥 ] − [𝑦𝑝𝑧 , 𝑥𝑝𝑧 ] − [𝑧𝑝𝑦 , 𝑧𝑝𝑥 ] + [𝑧𝑝𝑦 , 𝑥𝑝𝑧 ]
= [𝑦𝑝𝑧 𝑧𝑝𝑥 − 𝑧𝑝𝑥 𝑦𝑝𝑧 ] − [𝑦𝑝𝑧 𝑥𝑝𝑧 − 𝑥𝑝𝑧 𝑦𝑝𝑧 ] − [𝑧𝑝𝑦 𝑧𝑝𝑥 − 𝑧𝑝𝑥 𝑧𝑝𝑦 ] + [𝑧𝑝𝑦 𝑥𝑝𝑧 − 𝑥𝑝𝑧 𝑧𝑝𝑦 ]
= 𝑦[𝑝𝑧 𝑧 − 𝑧𝑝𝑧 ]𝑝𝑥 − [𝑦𝑥𝑝𝑧 𝑝𝑧 − 𝑥𝑦𝑝𝑧 𝑝𝑧 ] − [𝑧𝑧𝑝𝑦 𝑝𝑥 − 𝑧𝑧𝑝𝑥 𝑝𝑦 ] + 𝑥[𝑧𝑝𝑧 − 𝑝𝑧 𝑧]𝑝𝑦
= 𝑦[𝑝𝑧 , 𝑧]𝑝𝑥 − [𝑥𝑦𝑝𝑧 𝑝𝑧 − 𝑥𝑦𝑝𝑧 𝑝𝑧 ] − [𝑧𝑧𝑝𝑦 𝑝𝑥 − 𝑧𝑧𝑝𝑥 𝑝𝑦 ] + 𝑥[𝑧, 𝑝𝑧 ]𝑝𝑦
= 𝑦[𝑝𝑧 , 𝑧]𝑝𝑥 − 0 − 0 + 𝑥[𝑧, 𝑝𝑧 ]𝑝𝑦 ∴ [𝑝̂𝑧 , 𝑧̂ ] = −𝑖ℏ & ∴ [𝑧̂, 𝑝̂𝑧 ] = 𝑖ℏ
= 𝑦[−𝑖ℏ]𝑝𝑥 + 𝑥[𝑖ℏ]𝑝𝑦
= 𝑖ℏ[−𝑦𝑝𝑥 + 𝑥𝑝𝑦 ]
= 𝑖ℏ[𝑥𝑝𝑦 − 𝑦𝑝𝑥 ] ∴ 𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
= 𝑖ℏ𝐿̂𝑧
⇒ [𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ℏ𝐿̂𝑧
[𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝑖ℏ𝐿̂𝑥
[𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝑖ℏ𝐿̂𝑦
Hence
[𝐿̂𝑥 , 𝐿̂𝑥 ] = [𝐿̂𝑦 , 𝐿̂𝑦 ] = [𝐿̂𝑧 , 𝐿̂𝑧 ] = 0 Same commutes.
𝐴𝑙𝑠𝑜
[𝐿̂𝑦 , 𝐿̂𝑥 ] = −𝑖ℏ𝐿̂𝑧 Different do not commutes.
[𝐿̂𝑧 , 𝐿̂𝑦 ] = −𝑖ℏ𝐿̂𝑥

[𝐿̂𝑥 , 𝐿̂𝑧 ] = −𝑖ℏ𝐿̂𝑦
3. ̂ and Orbital angular Momentum 𝑳̂ :

Position 𝑿
Since we know that
𝐿̂𝑥 = (𝑦𝑝𝑧 − 𝑧𝑝𝑦 )𝑖̂ ∶ 𝐿̂𝑦 = (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂ ∶ 𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
(ii) [𝑥̂, 𝐿̂𝑦 ] = 𝑖ℏ𝑧̂

𝑅. 𝐻. 𝑆
= [𝑥̂, 𝐿̂𝑦 ]
= [𝑥̂, 𝑧̂ 𝑝𝑥 − 𝑥̂𝑝𝑧 ]
= [𝑥̂, 𝑧̂ 𝑝𝑥 ] − [𝑥̂, 𝑥̂𝑝𝑧 ]
= [𝑥̂𝑧̂𝑝𝑥 − 𝑧𝑝𝑥 𝑥̂] − [𝑥̂𝑥̂𝑝𝑧 − 𝑥̂𝑝𝑧 𝑥̂]
= [𝑥̂𝑧̂𝑝𝑥 − 𝑧𝑝𝑥 𝑥̂] − [𝑥̂𝑥̂𝑝𝑧 − 𝑥̂𝑥̂𝑝𝑧 ]
= 𝑧̂ [𝑥̂𝑝𝑥 − 𝑝𝑥 𝑥̂] − 0
= 𝑧̂ [𝑥̂, 𝑝𝑥 ] ∴ [𝑥̂, 𝑝̂𝑥 ] = 𝑖ℏ
= 𝑧̂ [𝑖ℏ]
⇒ [𝑥̂, 𝐿̂𝑦 ] = 𝑖ℏ𝑧̂
[𝑦̂, 𝐿̂𝑧 ] = 𝑖ℏ𝑥̂
[𝑧̂ , 𝐿̂𝑥 ] = 𝑖ℏ𝑦̂
Hence
[𝑥̂, 𝐿̂𝑥 ] = [𝑦̂, 𝐿̂𝑦 ] = [𝑧̂, 𝐿̂𝑧 ] = 0 Same commutes.
𝐴𝑙𝑠𝑜
[𝐿̂𝑦 , 𝑥̂] = −𝑖ℏ𝑧̂ or [𝑦, 𝐿𝑥 ] = −𝑖ℏ𝑧̂
[𝐿̂𝑧 , 𝑦̂] = −𝑖ℏ𝑥̂ or [𝑧̂ , 𝐿̂𝑦 ] = −𝑖ℏ𝑥̂
[𝐿̂𝑥 , 𝑧̂ ] = −𝑖ℏ𝑦̂ or [𝑥̂, 𝐿̂𝑧 ] = −𝑖ℏ𝑦̂
4. Linear and Orbital angular Momentum 𝑷 ̂ & 𝑳̂ :

Since we know that
𝐿̂𝑥 = (𝑦𝑝𝑧 − 𝑧𝑝𝑦 )𝑖̂ ∶ 𝐿̂𝑦 = (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂ ∶ 𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
(iii) [𝑝
̂, ̂
𝑥 𝐿𝑦 ] = 𝑖ℏ𝑝̂
𝑅. 𝐻. 𝑆
= [𝑝̂𝑥 , 𝐿̂𝑦 ]
= [𝑝̂𝑥 , 𝑧𝑝𝑥 − 𝑥𝑝𝑧 ]
= [𝑝̂𝑥 , 𝑧̂ 𝑝𝑥 ] − [𝑝̂𝑥 , 𝑥̂𝑝𝑧 ]
= [𝑝̂𝑥 𝑧̂ 𝑝𝑥 − 𝑧̂ 𝑝𝑥 𝑝̂𝑥 ] − [𝑝̂𝑥 𝑥̂𝑝𝑧 − 𝑥̂𝑝𝑧 𝑝̂𝑥 ]
= [𝑧̂𝑝̂𝑥 𝑝𝑥 − 𝑧̂ 𝑝𝑥 𝑝̂𝑥 ] − 𝑝𝑧 [𝑝̂𝑥 𝑥̂ − 𝑥̂𝑝̂𝑥 ]
= 0 − 𝑝𝑧 [𝑝̂𝑥 , 𝑥̂]
= −𝑝𝑧 [−𝑖ℏ] ∴ [𝑝̂𝑥 , 𝑥̂] = −𝑖ℏ
= 𝑖ℏ𝑝𝑧
⇒ [𝑝̂, ̂
𝑥 𝐿𝑦 ] = 𝑖ℏ𝑝𝑧
[𝑝̂𝑦 , 𝐿̂𝑧 ] = 𝑖ℏ𝑝𝑥
[𝑝̂𝑧 , 𝐿̂𝑥 ] = 𝑖ℏ𝑝𝑦
Hence
[𝑝̂𝑥 , 𝐿̂𝑥 ] = [𝑝̂𝑦 , 𝐿̂𝑦 ] = [𝑝̂𝑧 , 𝐿̂𝑧 ] = 0 Same commutes.
5. ̂ & 𝑳̂𝟐 :
Position and angular Momentum 𝑿
Since
𝐿2 = 𝐿2𝑥 + 𝐿2𝑦 + 𝐿2𝑧
(i) [𝑦, 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑧 − 𝑧𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]

𝑅. 𝐻. 𝑆
= [𝑦, 𝐿2 ]
= [𝑦, 𝐿2𝑥 + 𝐿2𝑦 + 𝐿2𝑧 ]
= [𝑦, 𝐿2𝑥 ] + [𝑦, 𝐿2𝑦 ] + [𝑦, 𝐿2𝑧 ]
= 𝐿𝑥 [𝑦, 𝐿𝑥 ] + [𝑦, 𝐿𝑥 ]𝐿𝑥 + 𝐿𝑦 [𝑦, 𝐿𝑦 ] + [𝑦, 𝐿𝑦 ]𝐿𝑦 + 𝐿𝑧 [𝑦, 𝐿𝑧 ] + [𝑦, 𝐿𝑧 ]𝐿𝑧
= 𝐿𝑥 [−𝑖ℏ𝑧̂ ] + [−𝑖ℏ𝑧̂ ]𝐿𝑥 + 𝐿𝑦 [0] + [0]𝐿𝑦 + 𝐿𝑧 [𝑖ℏ𝑥̂] + [𝑖ℏ𝑥̂]𝐿𝑧
= 𝐿𝑥 [−𝑖ℏ𝑧̂ ] + [−𝑖ℏ𝑧̂ ]𝐿𝑥 + 𝐿𝑧 [𝑖ℏ𝑥̂] + [𝑖ℏ𝑥̂]𝐿𝑧
= 𝑖ℏ[−𝐿𝑥 𝑧 − 𝑧𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]
⇒ [𝑦, 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑧 − 𝑧𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]
[𝑥, 𝐿2 ] = 𝑖ℏ[𝐿𝑦 𝑧 + 𝑧𝐿𝑦 − 𝐿𝑧 𝑦 − 𝑦𝐿𝑧 ]
[𝑧, 𝐿2 ] = 𝑖ℏ[𝐿𝑥 𝑦 + 𝑦𝐿𝑥 − 𝐿𝑦 𝑥 − 𝑥𝐿𝑦 ]
6. ̂ & 𝑳̂𝟐 :
Linear Momentum and angular Momentum 𝑷
[𝑝𝑦 , 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑝𝑧 − 𝑝𝑧 𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]

[𝑝𝑧 , 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑝𝑦 − 𝑝𝑦 𝐿𝑥 − 𝐿𝑦 𝑃𝑥 − 𝑝𝑥 𝐿𝑦 ]
7. Lowering and Raising Operators 𝑳̂+ & 𝑳̂− :

Since
𝐿+ = 𝐿𝑥 + 𝑖𝐿𝑦 ∶ 𝐿− = 𝐿𝑥 − 𝑖𝐿𝑦
[𝐿+ , 𝐿− ] = 2ℏ𝐿𝑧
8. ̂+ & 𝒂
Lowering and Raising ladder Operators 𝒂 ̂:
1
̂− , 𝒂
[𝒂 ̂+ ] = ℏ𝜔
2
1
̂+ , 𝒂
[𝒂 ̂− ] = − ℏ𝜔
2
Quantum Mechanics is a completely indeterministic theory.

Asking about the position or momentum of an electron, one
cannot get a definite answer; only a probabilistic answer is
possible. It is an open challenge to you there is always be the
uncertainty (multiple of ℏ)
1.37 What is The Uncertainty Principle?
It is not possible to measure two observables (𝐴̂ & 𝐵̂ ) simultaneously to an infinite accuracy.
It is impossible to devise an experiment that can measure simultaneously two (complementary) variables to unlimited accuracy.
It states that if two variables are represented by the two Hermitian operators A and B, and these operators do not commute
(𝐴̂𝐵̂ − 𝐵̂𝐴̂ ≠ 0), then it is impossible to simultaneously (exactly) measure the two variables.
The generalized form of uncertainty principle is given as,
1 2
𝜎𝐴2 𝜎𝐵2 ≥ ( [𝐴̂, 𝐵̂]) _____ (A)
2𝑖
̂&𝑩
Where 𝑨 ̂ are observables and 𝝈𝑨 & 𝝈𝑩 are standard deviation.
 Position-Momentum Uncertainty Relation

The uncertainty relations for position and momentum can be written as follows,
If observable are [𝑥̂, 𝑝̂𝑦 ] = 𝑖ℏ , Eq—(A) becomes
1 2
1 𝟐
ℏ 𝟐
𝜎𝑥2 𝜎𝑝2 ≥ ( [𝑥̂, 𝑝̂𝑦 ]) = ( 𝑖ℏ) = ( )
2𝑖 2𝑖 2
Since standard deviation are by nature positive
ℏ ℏ
𝜎𝑥 𝜎𝑝 ≥ or 𝛥𝑥. 𝛥𝑝 ≥
2 2
 Energy-Time Uncertainty Relation

Similarly the uncertainty relations for observables Energy and Time as,
ℏ
𝛥𝑡. 𝛥𝐸 ≥
2
 Another interesting application of the uncertainty relation is to the orbital angular momentum of a particle.
[𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ℏ𝐿̂𝑧 from Eq.(A)
1
̂𝑧 > |
Δ𝐿𝑥 Δ𝐿𝑦 ≥ ℏ | < 𝐿
2
1.38 What are the Application of One Dimensional SWE?

We will apply the Schrödinger equation to various one-dimensional potentials 𝑽(𝒙) and we shall investigate the interaction of a
particle with one-dimensional potentials
 The free particle,
 The potential step,
 The finite potential wells
 Infinite potential wells
 The harmonic oscillator.
The Time Independent Schrödinger equation describing the dynamics of a particle in a one-dimensional is given by,
ℏ2 𝜕 2
− Ψ(x) + 𝑉(𝑥)Ψ(x) = 𝐸̂ Ψ(x)
2𝑚 𝜕 2 𝑥
Similarly, the solutions of the Time Independent Schrödinger equation for time-independent potentials are stationary states.
𝑖𝐸𝑡
Ψ(𝑥, 𝑡) = 𝜓(𝑥) 𝑒 − ℏ
The Application of the Schrödinger equation
to one-dimensional problems enables us to
compare the predictions of classical and
quantum mechanics.
Free Particle: (free everywhere)
If the particle is not in the external field then it will be a free particle and its potential (energy) will be zero. 𝑉(𝑥) = 0
Particle is said to be in non-bound state. i.e Electron in conduction band, Electron gas in metals etc.
Then Time Independent Schrödinger wave equation for free particle become as,
ℏ2 𝜕 2
− Ψ(x) = 𝐸̂ Ψ(x)
2𝑚 𝜕 2 𝑥
Similarly, the solutions of the Schrödinger equation for free particle will as.
+∞
1
Ψ(𝑥, 𝑡) = ∫ 𝜓(𝑥, 0) 𝑒 −𝑖𝑘𝑥 𝑑𝑥
√2𝜋 −∞
 The physical solutions of the Schrödinger equation are thus given by wave packets, not by stationary solutions
1. The Potential Step:
A type of the potential in which potential quickly become either repulsive or attractive beyond a particular point (x=0) in order to
bound the free particle.
A potential step can be thought of a potential energy step which a particle has to overcome to become free.
A potential step is the vertical line plot in graph between potential V(x) and position (x).
e.g The elements of a tube in which an electron approaches a region with a negative electric potential.
Its mathematical equation is given as

0, 𝑥 < 0 (𝐿𝑒𝑓𝑡)
𝑉(𝑥) = {
𝑉0 , 𝑥 > 0(𝑅𝑖𝑔ℎ𝑡)
 Case – 1: 𝑬 > 𝑽𝟎
When particle all having the same mass and same velocity moving from left to right such that their energy E is greater than potential
step 𝑉0
 Classically, the particles approach the potential step or barrier 𝑉0 from the left and penetrate
through it to right. None of the particles get reflected. So there will be total transmission.
 But Quantum mechanics says that even particles has sufficient energy E higher than potential
step 𝑉0 then it is possible that there will be reflection through potential step 𝑉0 to the right.
 Case – 2: 𝑬 < 𝑽𝟎 (Tunneling)

When particle all having the same mass and same velocity moving from left to right such that their energy E is smaller than potential
step 𝑉0 .
 Classically, the particles arriving at potential step or barrier 𝑉0 from the left will come to a
stop. None of the particles will make it into the right side of the barrier there is total
reflection of the particles
 But Quantum mechanically there is a non-zero probability that the wave function penetrates
this potential step or barrier 𝑉0 .
 Tunneling effect:
The quantum mechanical effect which is due to the wave aspect of microscopic objects can
tunnel through classically impenetrable barriers known as the tunneling effect.
2. The Potential Barrier and Well:
A type of the potential in which potential quickly become either repulsive or attractive beyond a particular point (x=0) in order to
bound the free particle.
Its mathematical equation is given as

0, 𝑥 < 0 (𝐿𝑒𝑓𝑡)
𝑉(𝑥) = { 𝑉0 , 0≤𝑥≤𝑎
0, 𝑥 > 𝑎 (𝑅𝑖𝑔ℎ𝑡)
 Case – 1: 𝑬 > 𝑽𝟎
step 𝑉0
 Classically, the particles approach the potential step or barrier 𝑉0 from the left and penetrate
through it to right. None of the particles get reflected. So there will be total transmission.
 But Quantum mechanics says that even particles has sufficient energy E higher than
potential step 𝑉0 then it is possible that there will be reflection through potential step 𝑉0 to
the right.
Wavefunction across the three region will be as
𝜓1 (𝑥) = 𝐴𝑒 𝑖𝑘1𝑥 + 𝐵𝑒 −𝑖𝑘1𝑥 ; 𝑥 ≤ 0 (𝐿𝑒𝑓𝑡)

𝜓(𝑥) = { 𝜓2 (𝑥) = 𝐶𝑒 𝑖𝑘2 𝑥 + 𝐷𝑒 −𝑖𝑘2 𝑥 ; 0 ≤ 𝑥 ≤ 𝑎
𝜓3 (𝑥) = 𝐸𝑒 𝑖𝑘1 𝑥 ; 𝑥 ≥ 𝑎 (𝑅𝑖𝑔ℎ𝑡)
 Transmission coefficient T give the probability of transmitted particle through potential barrier of potential 𝑉0 .
∗
𝐸 𝐸
𝑇 = ( )( )
𝐴 𝐴
4𝐾12 𝐾22
𝑇=
4𝐾1 𝐾2 𝑐𝑜𝑠𝑘2 𝛼 + (𝐾12 +𝐾22 )2 𝑠𝑖𝑛𝑘2 𝛼
2 2
 Reflection coefficient R give the probability of reflected particle through potential barrier of potential 𝑉0 .
𝐵 𝐵 ∗
𝑅 = ( )( )
𝐴 𝐴
(𝐾12 −𝐾22 )2 𝑠𝑖𝑛𝑘2 𝛼
𝑅=
4𝐾12 𝐾22 𝑐𝑜𝑠𝑘2 𝛼 + (𝐾12 +𝐾22 )2 𝑠𝑖𝑛𝑘2 𝛼
 Such that sum of probability of Transmission coefficient and Reflection coefficient is equal to 1 or 100%.
𝑅+𝑇 =1
 Special case For 𝐸 ≫ 𝑉0 , 𝑇 ≅ 1 & 𝑅 ≅ 0 𝑠𝑢𝑐ℎ 𝑡ℎ𝑎𝑡 𝑅 + 𝑇 = 1
 Case – 2: 𝑬 < 𝑽𝟎 (Tunneling)

step 𝑉0
 Classically, the particles arriving at the potential step from the left will come to a stop at x =0
and then all will bounce back to the left. So there is total transmission.
 But Quantum mechanics says that even particles has sufficient energy E smaller than potential
step 𝑉0 then it is possible that there will be transmission through the potential toward right.
The quantum mechanical effect which is due to the wave aspect of microscopic objects can
tunnel through classically impenetrable barriers known as the tunneling effect.
Wavefunction across the three region will be as
𝜓1 (𝑥) = 𝐴𝑒 𝑖𝑘1𝑥 + 𝐵𝑒 −𝑖𝑘1𝑥 ; 𝑥 ≤ 0 (𝐿𝑒𝑓𝑡)

𝜓(𝑥) = { 𝜓2 (𝑥) = 𝐶𝑒 𝑘2𝑥 + 𝐷𝑒 𝑘2𝑥 ; 0 ≤ 𝑥 ≤ 𝑎
𝜓3 (𝑥) = 𝐸𝑒 𝑖𝑘1 𝑥 ; 𝑥 ≥ 𝑎 (𝑅𝑖𝑔ℎ𝑡)
 Transmission coefficient T give the probability of transmitted particle through potential barrier of potential 𝑉0 .
𝐸 𝐸 ∗
𝑇 = ( )( )
𝐴 𝐴
2 −1
1 𝐾12 +𝐾22
𝑇 = ⌊1 + ( ) 𝑠𝑖𝑛ℎ2 (𝑘2 𝛼)⌋
4 𝑘1 𝑘2
 Reflection coefficient R give the probability of reflected particle through potential barrier of potential 𝑉0 .
𝐵 𝐵 ∗
𝑅 = ( )( )
𝐴 𝐴
2
1 𝐾12 +𝐾22
𝑅 = 𝑇( ) 𝑠𝑖𝑛ℎ2 (𝑘2 𝛼)
4 𝑘1 𝑘2
 Such that sum of probability of Transmission coefficient and Reflection coefficient is equal to 1 or 100%.
𝑅+𝑇 =1
 Special case , For 𝐸 ≪ 𝑉0 , 𝑇 ≅ 0 & 𝑅 ≅ 1 𝑠𝑢𝑐ℎ 𝑡ℎ𝑎𝑡 𝑅 + 𝑇 = 1
3. The Infinite Square Potential Well: (infinitely deep asymmetric potential well)
A infinite square potential well in one dimension is a problem in quantum mechanics in which particle is bound between two walls of
infinite potential 𝑖. 𝑒(−∞ 𝑡𝑜 + ∞)
The mathematical equation can be given as
+∞ , 𝑥 < 0 (𝐿𝑒𝑓𝑡)
0, 0≤𝑥≤𝑎
𝑉(𝑥) = { 0 , 0≤𝑥≤𝑎 𝑜𝑟 𝑉(𝑥) = {
∞, 𝑜𝑡ℎ𝑒𝑟𝑤𝑖𝑠𝑒
+∞ , 𝑥 > 𝑎 (𝑅𝑖𝑔ℎ𝑡)
 Classically, the particle remains confined inside the well, moving at constant momentum back and forth as a result of
repeated reflections from the walls of the well.
 Quantum mechanically, we expect this particle to have only bound state solutions.
 Outside the well, 𝝍(𝒙) = 𝟎 & 𝑽 = 𝑰𝒏𝒇𝒊𝒏𝒊𝒕𝒆

Because outside the well the probability of finding the particle is zero
 Inside the well, 𝝍(𝒙) ≠ 𝟎 & 𝑽 = 𝟎

Particle possess minimum energy called Zero point energy.
Zero point energy:
Zero point energy is the minimum energy which a bound particle possess in the well 0 ≤ 𝑥 ≤ 𝑎.
Its value is finite and always greater than zero.
The zero-point energy of bound state systems cannot be zero, otherwise it would violate the uncertainty principle.
i.e 𝐸 = 𝑛ℎ𝑓 here n=0 can never be possible so E=0 is also not possible but n=1 is possible so E always have value greater
than zero.
 Energy of particle inside the well 0 ≤ 𝑥 ≤ 𝑎

The energy is quantized; only certain values are permitted
𝑛 2 ℎ2 𝜋 2
𝐸= (𝑛 = 1,2,3,4, … . )
2𝑚𝑎2
 Wave function or solution of particle inside the well 0 ≤ 𝑥 ≤ 𝑎

2 𝑛𝜋
𝜓𝑛 = √ sin ( 𝑥)
𝑎 𝑎
 The Harmonic Oscillator:
The harmonic oscillator which provides a model for vibrational phenomena of the Microscopic particles.
The solution of Harmonic oscillator can be solved by two methods

1) Using Schrödinger wave equation method.
2) Using Analytical method (or Raising 𝒂+ and lowering ladder 𝒂− operators.)
The potential of harmonic oscillator is given as

1
𝑉 = 𝑚𝜔2 𝑥 2
2
 Schrödinger wave equation method.

The time independent Schrodinger wave equation become,
ℏ 𝜕2 1
− 2
𝜓(𝑥) + 𝑚𝜔2 𝑥 2 𝜓(𝑥) = 0
2𝑚 𝜕𝑥 2
Energy of Harmonic oscillator is ,
1
𝐸 = (𝑛 + ) ℏ𝜔 (𝑛 = 1,2,3,4,5, … . . )
2
 Analytic or ladder method.

For finding solution of Harmonic oscillator we here operate 𝒂± ladder operators.
 𝒂± ladder operators:
These operators allow the energy to climb up and down every time by ℏ𝜔.
𝒂+ is Raising Ladder Operator it increases the energy every time by ℏ𝜔 and particle transits one state upward.
𝒂− is Raising Ladder Operator it decreases the energy every time by ℏ𝜔 and particle transits one state downward.
1 ℏ 𝑑 1 ℏ 𝑑
𝑎+ = + 𝑖𝑚𝜔𝑥 ∶ 𝑎− = − 𝑖𝑚𝜔𝑥
√2𝑚 𝑖 𝑑𝑥 √2𝑚 𝑖 𝑑𝑥
𝑚𝜔 2
𝜓𝑛 = 𝐴𝑛 (𝑎+ )𝑛 𝑒 − 2ℏ 𝑥 &
Q. What if the lowering ladder operator apply repeatedly or 𝑎− 𝜓0 = 0?

The particle will reaches to its lowest energy state or lowest rung or ground state 𝜓0 of energy 𝐸0 .
1
𝐸𝑜 = ( ) ℏ𝜔 𝑓𝑜𝑟 𝑛 = 0
2
And particle attained the energy less than zero which is not possible. T his would imply that we know simultaneously and
with absolute precision both the position and the momentum of the system. This would contradict the uncertainty principle.
So there is big flaw in the theory of ladder operator on applying SHM.
1.39 What is Angular Momentum?

 After treating one-dimensional problems in we now should deal with three-dimensional problems. Such three dimensional
problem cannot be understood without concept of Angular momentum. 𝑽 = 𝑽(𝒓)
 Also electrons revolve in atoms around nucleus so it will be significant.
Angular momentum is the cross product of position 𝑟⃗ and momentum 𝑝⃗.
𝐿̂ = 𝑟⃗ × 𝑝⃗ = −𝑖ℏ 𝑟⃗ × ⃗∇⃗
𝐿̂ = 𝑟̂ × 𝑝̂ = (𝑦𝑝𝑧 − 𝑧𝑝𝑧 )𝑖̂ + (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂ + (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
Where
𝐿̂𝑥 = (𝑦𝑝𝑧 − 𝑧𝑝𝑦 )𝑖̂
𝐿̂𝑦 = (𝑧𝑝𝑥 − 𝑥𝑝𝑧 )𝑗̂
𝐿̂𝑧 = (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘̂
And
𝐿2 = 𝐿2𝑥 + 𝐿2𝑦 + 𝐿2𝑧
1.40 What is representation of Angular Momentum in Spherical polar co-ordinates ?
𝜕 1 𝜕
𝐿⃗⃗ = −𝑖ℏ ( 𝜙̂ − 𝜃̂)
𝜕𝜃 𝑠𝑖𝑛𝜃 𝜕𝜙
ℏ 𝜕 𝜕
𝐿̂𝑥 = 𝑖̂. 𝐿⃗⃗ = (−𝑠𝑖𝑛𝜙 − 𝑐𝑜𝑠𝜙 𝑐𝑜𝑡𝜃 )
𝑖 𝜕𝜃 𝜕𝜙
ℏ 𝜕 𝜕
𝐿̂𝑦 = 𝑗̂. 𝐿⃗⃗ = (𝑐𝑜𝑠𝜙 − 𝑠𝑖𝑛𝜙 𝑐𝑜𝑡𝜃 )
𝑖 𝜕𝜃 𝜕𝜙
𝑑
𝐿̂𝑧 = 𝑘̂. 𝐿⃗⃗ = −𝑖ℏ
𝑑𝜙
1.41 Eigenvalue and Eigenfunction of 𝑳̂𝒛 Angular Momentum?
𝐿̂𝑧 Angular momentum represent the spin motion of particle.
𝑑
𝐿̂𝑧 = −𝑖ℏ
𝑑𝜙
𝐿𝑧 𝜓 = 𝑚ℏ𝜓
Eigen value of 𝐿̂𝑧 angular momentum is,
𝜆 = 𝑚ℏ
Eigenfunction of 𝐿̂𝑧 Angular Momentum
𝑖𝜆
𝜓 = 𝐴𝑒 ℏ 𝜙
1.42 What is Raising 𝑳̂+ and Lowering 𝑳̂− operators?

 Raising operators 𝑳̂+ : which step up one state of particle.
𝐿̂+ = 𝐿̂𝑥 + 𝑖𝐿̂𝑦
 Lowering operators 𝑳̂− : which step down one state of particle.
𝐿̂− = 𝐿̂𝑥 − 𝑖𝐿̂𝑦
 Commutation relations of 𝑳̂+ & 𝑳̂− :

[𝐿+ , 𝐿− ] = 2ℏ𝐿𝑧
 Effect of 𝑳̂+ & 𝑳̂− on eigen vaule 𝑳̂𝒛 :
Raising operators 𝐿̂+ :
𝐿𝑧 (𝐿+ 𝜓) = (𝑚 + 1)ℏ(𝐿+ 𝜓)
Lowering operators 𝐿̂− :
𝐿𝑧 (𝐿− 𝜓) = (𝑚 + 1)ℏ(𝐿− 𝜓)
 Effect of 𝑳̂+ & 𝑳̂− on eigen vaule 𝑳𝟐 :

Raising operators 𝐿̂+ :
𝐿2 (𝐿+ 𝜓) = 𝑎(𝐿+ 𝜓)
Lowering operators 𝐿̂− :
𝐿2 (𝐿− 𝜓) = 𝑎(𝐿− 𝜓)
1.43 Eigenvalue 𝑳𝟐 Angular Momentum?
𝐿2 𝜓 = ℏ2 𝑙(𝑙 + 1)𝜓
Eigen value of 𝐿̂𝑧 angular momentum is,
𝜆 = ℏ2 𝑙(𝑙 + 1)
Some important relation as,
 𝐿𝑧 𝜓 = 𝑚ℏ𝜓
 𝐿2 𝜓 = ℏ2 𝑙(𝑙 + 1)𝜓
 𝐿𝜓 = ℏ√𝑙(𝑙 + 1)𝜓
1.44 Matrix Representation of angular momentum?

 𝑳𝒛 :
ℏ 0 0 1 0 0
𝐿𝑧 = (0 0 0 ) = ℏ (0 0 0)
0 0 −ℏ 0 0 −1
 𝑳𝟐 :
2ℏ2 0 0 1 0 0
2
𝐿 =( 0 2ℏ2 0 ) = 2ℏ2 (0 1 0)
0 0 2ℏ2 0 0 1
 𝑳:
1 0 0
𝐿 = √2ℏ (0 1 0)
0 0 1
 𝑳̂+
0 1 0
𝐿+ = √2ℏ (0 0 1)
0 0 0
 𝑳̂−
0 0 0
𝐿− = √2ℏ (0 0 1)
0 1 0
1.45 Define the Quantum Mechanics in 3-Dimensions?

 Linear Momentum Operator:
𝜕 𝜕 𝜕
̂ ∶ 𝑤ℎ𝑒𝑟𝑒 , ∇
𝑝̂ = −𝑖ℏ∇ ̂= 𝑖̂ + 𝑗̂ + 𝑘̂
𝜕𝑥 𝜕𝑦 𝜕𝑧
 Time Independent Schrödinger Wave Equation:
ℏ2 2
− ∇ 𝜓𝑛 + 𝑉𝜓𝑛 = 𝐸𝑛 𝜓𝑛
2𝑚
ℏ2 1 𝑑 2 𝑋 ℏ2 1 𝑑 2 𝑌 ℏ2 1 𝑑 2 𝑍
[− 2
+ 𝑉(𝑥)] + [− 2
+ 𝑉(𝑦)] + [− + 𝑉(𝑧)] = 𝐸𝑥 𝜓𝑛 + 𝐸𝑦 𝜓𝑛 + 𝐸𝑧 𝜓𝑛
2𝑚 X 𝑑𝑥 2𝑚 Y 𝑑𝑥 2𝑚 Z 𝑑𝑥 2
Where, 𝑉(𝑟) = 𝑉(𝑥, 𝑦, 𝑧) = 𝑉𝑥 (𝑥) + 𝑉𝑦 (𝑦) + 𝑉𝑧 (𝑧) ∶ 𝐸 = 𝐸𝑥 + 𝐸𝑦 + 𝐸𝑧
The Box Potential:

There are two types of box potentials as,
1. The Rectangle Box Potential:
The potential in 3-Dimension is given as,
0, 0 < 𝑥 < 𝑎, 0 < 𝑥 < 𝑏 ,0 < 𝑥 < 𝑐

𝑉(𝑥, 𝑦, 𝑧) = {
∞ 𝑒𝑙𝑠𝑒𝑤ℎ𝑒𝑟𝑒
The wave function in 3-Dimension is given as,
8 𝑛𝑥 𝜋 𝑛𝑦 𝜋 𝑛𝑧 𝜋
𝜓𝑛𝑥𝑛𝑦𝑛𝑧 (𝑥,𝑦,𝑧) = √ 𝑠𝑖𝑛 ( 𝑥) 𝑠𝑖𝑛 ( 𝑦) 𝑠𝑖𝑛 ( 𝑧)
𝑎𝑏𝑐 𝑎 𝑏 𝑐
The Energy in 3-Dimension is given as,
ℏ2 𝜋 2 𝑛𝑥2 𝑛𝑦2 𝑛𝑧2

𝐸𝑛𝑥𝑛𝑦𝑛𝑧 = ( + + )
2𝑚 𝑎2 𝑏 2 𝑐 2
2. The Cubic Potential:
Similarly,
ℏ2 𝜋 2 2
𝐸𝑛𝑥𝑛𝑦 𝑛𝑧 = (𝑛 + 𝑛𝑦2 + 𝑛𝑧2 ), 𝑛𝑥 , 𝑛𝑦 , 𝑛𝑧 = 1,2,3, … . .
2𝑚𝐿2 𝑥
8 𝑛𝑥 𝜋 𝑛𝑦 𝜋 𝑛𝑧 𝜋
𝜓𝑛𝑥𝑛𝑦𝑛𝑧 (𝑥,𝑦,𝑧) = √ 3 𝑠𝑖𝑛 ( 𝑥) 𝑠𝑖𝑛 ( 𝑦) 𝑠𝑖𝑛 ( 𝑧)
𝐿 𝐿 𝐿 𝐿
3. The Hydrogen Atom:
The hydrogen atom consists of an electron and a proton. For simplicity, we will ignore their spins. The electron of charge 𝑒 circles
around the proton by a mutual attraction given by the Coulomb’s Law as
𝑒 1
𝑉(𝑟) = −
4𝜋𝜖0 𝑟
The time-dependent Schrödinger equation for the hydrogen atom is given by
ℏ2 2 ℏ2 2 𝜕
[− ∇𝑝 − ∇𝑒 + 𝑉(𝑟)] Ψ(𝑟𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 , 𝑟𝑝𝑟𝑜𝑡𝑜𝑛 , 𝑡) = 𝑖ℏ Ψ(𝑟𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 , 𝑟𝑝𝑟𝑜𝑡𝑜𝑛 , 𝑡)
2𝑚 2𝑚 𝜕𝑥
ℏ 2 2 ℏ2 2 𝑒 1 𝜕
[− ∇𝑝 − ∇𝑒 + − ] Ψ(𝑟𝑒 , 𝑟𝑝 , 𝑡) = 𝑖ℏ Ψ(𝑟𝑒 , 𝑟𝑝 , 𝑡)
2𝑚 2𝑚 4𝜋𝜖0 𝑟 𝜕𝑥
The radial equation for Hydrogen atoms is as,
ℏ2 𝑑 2 𝑒 1 ℏ2 𝑙(𝑙 + 1)
− 2
𝑈(𝑟) + [− + ] 𝑈(𝑟) = 𝐸𝑈(𝑟)
2𝑚 𝑑𝑥 4𝜋𝜖0 𝑟 2𝑚 𝑟 2
The solution 𝑈(𝑟) of radial equation for Hydrogen atom is given as,
𝑈(𝑟) = 𝑟 𝑙+1 𝑓(𝑟)𝑒 −𝜆𝑟
And the energy quantization of hydrogen atom given as,
2
𝑚 𝑒2 1 𝐸1
𝐸𝑛 = − [− 2
( ) ] 2 = 2 , 𝑛 = 1,2,3, … .
2ℏ 4𝜋𝜖0 𝑛 𝑛
For 𝑛 = 1 or ground state the value of energy 𝐸1 become 𝐸1 = −13.6 𝑒𝑉
1.46 What is Many particle system?
Physical systems involve many particles are known as many-particle or many-body systems. e.g. (nucleons, nuclei, atoms, molecules,
solids, fluids, gases)
 Atomic, nuclear, and sub nuclear systems involve intermediate numbers of particles (2 to 300),
 Solids, fluids, and gases are truly many-body systems, since they involve very large numbers of particles (1023 ).
The wavefunction of N-particle system is given as
−𝑖𝐸𝑡
Ψ(𝑟1 , 𝑟2 , … . , 𝑟𝑁 , 𝑡) = 𝑒 ℏ 𝜓(𝑟1 , . , 𝑟𝑖 , . , 𝑟𝑗 . 𝑟𝑁, )
The TISWE is given as

𝜕
𝑖ℏ ̂ 𝛹(𝑟1 , 𝑟2 , … . , 𝑟𝑁 , 𝑡)
𝛹(𝑟1 , 𝑟2 , … . , 𝑟𝑁 , 𝑡) = 𝐻
𝜕𝑥
Here we will consider that all Identical

1.47 What are Identical Particles? particles are Non-interacting with each other.
The type of particle having same properties know as identical particle.
1. In Classical mechanics
 All the identical particles are distinguishable i.e. we can tag them or color them.
 All the identical are traceable i.e. we can follow the motion of each particle along the path.
Therefore identical classical particles, do not lose their identity and they are distinguishable.
2. In Quantum mechanics
 All the identical particles are indistinguishable i.e. we have no mechanism to tag the particles.
 All the identical are not traceable i.e. according to Heisenberg Uncertainty Principle.
Therefore identical Quantum particles, do lose identity and they are indistinguishable.
Two classical distinct configuration of two identical particle is on wire.

The probability density of the configuration in figure (a) is |𝝍(𝒙𝟏 , 𝒙𝟐 )|𝟐
In Quantum mechanics identical particle 1 and 2 are also indistinguishable so probability density
associated with these configuration will |𝝍(𝒙𝟐 , 𝒙𝟏 )|𝟐 and must be the same.
Thus |𝝍(𝒙𝟏 , 𝒙𝟐 )|𝟐 = |𝝍(𝒙𝟐 , 𝒙𝟏 )|𝟐
Symmetries: An operation performed on a system (as

represented by a unitary operator is a symmetry
operation if the evolution of the system is unaffected
by the operation
1.48 What is Interchange Symmetry of Identical particles?
A technique to interchange the position of ith and jth particle of many particle system in order to developed symmetric or anti-
symmetric wavefunction is known as Interchange symmetry.
 A Permutation or Exchange operator 𝑷𝒊𝒋 is as an operator that, when acting on an N-particle wave
function 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) interchanges its the ith and the jth particles.
𝑃̂𝑖𝑗 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) = ±𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 )
When we interchange ith and jth particles of system by Permutation or Exchange operator 𝑃𝑖𝑗 . The wave function of a system of N
identical particles 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) is either symmetric or antisymmetric wave function
𝑃̂𝑖𝑗 𝜓(𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) = ±𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 ) ___ Which corresponds to two values +𝜓𝑠 & − 𝜓𝑎𝑛
1. Symmetric wave function (+𝝍𝒔 ): (Boson)

Symmetric wave function is represented by positive sign wavefuction on interchanging particle ith and jth particles
𝜓𝑠 (𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) = +𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 )
Boson:
Symmetric wave functions corresponds to the particle with integral spin called Boson.
𝑆𝑖 = 0,1ℏ, 2ℏ, 3ℏ, … … . .
Bosons obey Bose–Einstein statistics. Here we will consider that all Identical particles are
e.g. photons, pions, alpha particles etc. Non-interacting with each other.
This implies that each particle moves in a common
potential 𝑽(𝒓𝟏 , . . , 𝒓𝒊 𝒓𝒋 , , , 𝒓𝑵 ) and wavefunction
Construction of symmetric wave functions 𝝍𝒔 : −𝒊𝑬𝒕
𝝍(𝒓𝟏 , , 𝒓𝒊 , . , 𝒓𝒋 , . 𝒓𝑵, 𝒕) = 𝒆 ℏ 𝝍(𝒓𝟏 , . , 𝒓𝒊 , . , 𝒓𝒋 . 𝒓𝑵, 𝒕)
We can construct symmetric wave functions of 2- particle system as,
1
𝜓𝑠 (𝑟1 , 𝑟2 ) = [𝜓𝑛1 (𝑟1 )𝜓𝑛2 (𝑟2 ) + 𝜓𝑛1 (𝑟2 )𝜓𝑛2 (𝑟1 )]
√2
For symmetric wave functions of N particle system as,
1
𝜓𝑠 (𝑟1 , 𝑟2 ) = ∑ 𝑃̂ 𝜓𝑛1 (𝑟1 )𝜓𝑛2 (𝑟2 ) … … 𝜓𝑛𝑁 (𝑟𝑁 )
√𝑁! 𝑝
2. Anti-symmetric wave function (−𝝍𝒂𝒏 ): (Fermion)

Symmetric wave function is represented by negative sign wavefuction on interchanging particle ith and jth particles
𝜓𝑎𝑛 (𝑟1 , . , . , 𝑟𝑖 , . , . , 𝑟𝑗 , . , . 𝑟𝑁 ) = −𝜓(𝑟1 , . , . , 𝑟𝑗 , . , . , 𝑟𝑖 , . , . 𝑟𝑁 )
Fermion:
Anti-symmetric wave functions corresponds to the particle with half odd integral spin called Fermion.
ℏ ℏ ℏ
𝑆𝑖 = ,3 , 5 , … … . .
2 2 2
Fermions are said to obey Fermi–Dirac statistics There are two kinds of Identical particle.
1. Boson for which use the plus sign
e.g. quarks, electrons, positrons, protons, neutrons etc.
2. Fermion for which we use minus sign.
3.
Construction of anti-symmetric wave functions 𝝍𝒂𝒏 : {
𝑎𝑙𝑙 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑤𝑖𝑡ℎ 𝑖𝑛𝑡𝑒𝑟𝑔𝑟𝑒 𝑠𝑝𝑖𝑛 𝑎𝑟𝑒 𝐵𝑜𝑠𝑜𝑛𝑠
𝑎𝑙𝑙 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑤𝑖𝑡ℎ ℎ𝑎𝑙𝑓 𝑖𝑛𝑡𝑒𝑟𝑔𝑟𝑒 𝑠𝑝𝑖𝑛 𝑎𝑟𝑒 𝐵𝑜𝑠𝑜𝑛𝑠
We can construct symmetric wave functions of 2- particle system as,
1
𝜓𝑎𝑛 (𝑟1 , 𝑟2 ) = [𝜓𝑛1 (𝑟1 )𝜓𝑛2 (𝑟2 ) − 𝜓𝑛1 (𝑟2 )𝜓𝑛2 (𝑟1 )]
√2
In determinant form as
1 𝜓𝑛1 (𝑟1 ) 𝜓𝑛1 (𝑟2 )

𝜓𝑎𝑛 (𝑟1 , 𝑟2 ) = | |
√2 𝜓𝑛2 (𝑟1 ) 𝜓𝑛2 (𝑟2 )
For symmetric wave functions of N particle system as,
1
𝜓𝑎𝑛 (𝑟1 , 𝑟2 ) = ∑ (−1)𝑃 𝑃̂ 𝜓𝑛1 (𝑟1 )𝜓𝑛2 (𝑟2 ) … … 𝜓𝑛𝑁 (𝑟𝑁 )
√𝑁! 𝑝
In determinant form as
𝜓𝑛1 (𝑟1 ) 𝜓𝑛1 (𝑟2 ) ⋯ 𝜓𝑛1 (𝑟𝑁 )

1
𝜓𝑎𝑛 (𝑟1 , 𝑟2 ) = | 𝜓𝑛2 (𝑟1 ) 𝜓𝑛2 (𝑟2 ) … 𝜓𝑛2 (𝑟𝑁 ) |
√𝑁! 𝜓 (𝑟 ) 𝜓𝑛𝑁 (𝑟2 ) … 𝜓𝑛𝑁 (𝑟𝑁 )
𝑛𝑁 1
This expression is known as the Slater determinant or Pauli Exclusion Principle.
Q. What is summarization postulate?

In nature, the wavefunction of systems containing N identical particles are either totally symmetric or totally anti-symmetric
by the interchanging ith and jth particles and that wavefunction with mixed symmetry do not exist.
Q. What is Pauli Exclusion principle?

In a system of N identical particles, no two fermions can occupy the same single-particle state at a time.
or
Every single-particle state can be occupied by at most one fermion. This is the Pauli exclusion principle,
Or
It states that no two electrons can occupy simultaneously the same (single-particle)
quantum state on the same atom there can be only one (or at most one) electron
occupying a state of quantum numbers
The exclusion principle plays an important role in the structure of atoms

Q. What is Boson Condensation?

There is no restriction on the number of bosons that can occupy a single state. Instead of the exclusion
principle of fermions, bosons tend to condense all in the same state, the ground state; this
is called boson condensation.
For instance, all the particles of liquid 𝐻𝑒 4 (a boson system) occupy the same ground
state. This phenomenon is known as Bose–Einstein condensation. The properties of
liquid 𝐻𝑒 3 are, however, completely different from those of liquid 𝐻𝑒 4 , because 𝐻𝑒 3
is a fermion system.
In quantum mechanics most of the problems cannot be

solved exactly because exact solutions of the Schrödinger
equation exist only for a few systems. So we use different
methods to solve Schrödinger equation which are known
as Approximation methods.
1.49 What are Approximation Methods for the Solution of SWE?

We use different methods to solve Schrödinger equation which are known as Approximation methods.
Approximation methods are the techniques for obtaining approximate solution to the Schrödinger equation.
 Application
Following are the application as
̂.
1. To the study Wavefunction 𝛹 of a (time-independent) Hamiltonian 𝐻
2. To the study Ground state energy 𝐸𝑔 .
3. To the study Bound state energy.
4. To the study Tunneling rate through potential barrier.
 Types
To study problems, we focus on three approximation methods:
1. Perturbation theory.
2. The variational method. (the energy eigenvalues of the ground state and the first few excited states of a system)
3. The WKB method.(the energy eigenvalues and wave functions of systems for which the classical limit is valid.)
1.50 What is Perturbation theory?
Perturbation theory is a systemic procedure for obtaining approximate solution to the perturbed problem by building on the
known exact solution to the unperturbed problem
Perturbation theory generate the approximation solution to the Schrödinger wave equation. Such solution appear in form of
expansion away from the known, unperturbed problem.
̂ of the perturbed problem is called the perturbation

The theory that seeks the approximate eigenstate of the total Hamiltonian H
theory.
Formula:
̂=𝐻
𝐻 ̂0 + 𝐻
̂𝑝  Unperturbed problems: Whose solutions are known
i.e. Particle in a Box
̂=𝐻
𝐻 ̂0 + 𝜆𝐻́
Where  Perturbed problems: Whose solution are not known i.e
̂ is Total Hamiltonian of Perturbed problem system of particle in atoms.
𝐻
̂0 is Hamiltonian of Unperturbed problem dependent on time
𝐻
̂&𝐻
𝐻 ̂0 𝑎𝑟𝑒 𝑣𝑒𝑟𝑦 𝑣𝑒𝑟𝑦 𝑐𝑙𝑜𝑠𝑒
̂𝑝 is the deviation or perturbation explicitly (independent or independent) on time
𝐻
𝜆 is the Dimensionless parameter (𝜆 ≪ 1)
Perturbation theory is based on the assumptions that the
 The (Perturbed) problem of Hamiltonian 𝐻 ̂ we wish to solve is only slightly different from a (Unperturbed) problem of
Hamiltonian 𝐻 ̂0 which is exactly solved and known. (𝐻̂≅𝐻 ̂0 )
 Considering very small deviation 𝐻 ̂𝑝 between these two problems is
 ̂𝑝 = 𝜆𝐻́ .
Calculating this deviation 𝐻
 Then adding this deviation as a correction to (Unperturbed) problem 𝐻 ̂0 .
̂=𝐻
𝐻 ̂0 + 𝐻
̂𝑝
̂=𝐻
𝐻 ̂0 + 𝜆𝐻́
Types
1. ̂𝑝 ≠ 𝐻
Time-Independent Perturbation Theory. 𝐻 ̂𝑝 (𝑡).
2. ̂𝑝 = 𝐻
Time-Dependent Perturbation Theory. 𝐻 ̂𝑝 (𝑡).
1.51 What is Time-Independent Perturbation theory?
̂𝑝 , has no explicit dependence on time 𝐻

The perturbation theory in which the Perturbation, 𝐻 ̂𝑝 ≠ 𝐻
̂𝑝 (𝑡). And unperturbed
Hamiltonian, H0, is time-independent.
̂=𝐻
𝐻 ̂0 + 𝐻
̂𝑝
̂=𝐻
𝐻 ̂0 + 𝜆𝐻́
Where
̂ is Total Hamiltonian of Perturbed problem
𝐻
̂0 is Hamiltonian of Unperturbed problem dependent on time
𝐻
̂&𝐻
𝐻 ̂0 𝑎𝑟𝑒 𝑣𝑒𝑟𝑦 𝑣𝑒𝑟𝑦 𝑐𝑙𝑜𝑠𝑒
̂𝑝 is the deviation or perturbation explicitly independent on time
𝐻
𝜆 is the Dimensionless parameter (𝜆 ≪ 1)
Types
̂0 are non-degenerate or degenerate. Each of these two

Consider two separate cases depending on whether the exact solutions of 𝐻
cases requires its own approximation scheme as follow
1. Non-degenerate Time-Independent Perturbation Theory

2. Degenerate Time-Independent Perturbation Theory
 Time-Independent Non-degenerate Perturbation theory
̂ 0 . i.e. In which two

The Time-Independent Perturbation Theory which has non-degenerate unperturbed Hamiltonian H
different unperturbed states shares the different energy.
Suppose the solved Schrodinger wave equation in 1-Dimension Potential Well is
 Non-degenerate sates: Two different states which

𝐻0 𝜓𝑛0 = 𝐸𝑛 𝜓𝑛0 share the different energy.
 Degenerate sates: Two different states which share the

same or equal energy.
When we perturbed potential slightly, the above equation become
𝐻𝜓𝑛 = 𝐸𝑛 𝜓𝑛
 Perturbation Expansion: The wavefuction 𝜓𝑛 and energy 𝐸𝑛 of perturbed Hamiltonian can be written as power series in 𝜆.
𝜓𝑛 = 𝜓𝑛0 + 𝜆𝜓𝑛1 + 𝜆2 𝜓𝑛2 + ⋯ ----(1)

𝐸𝑛 = 𝐸𝑛0 + 𝜆𝐸𝑛1 + 𝜆2 𝐸𝑛2 + ⋯ ----(2)
Here
o 𝜓𝑛0 is exactly solved/ known wavefuction of unperturbed Hamiltonian 𝐻0
o 𝐸𝑛0 is exactly solved /known energy unperturbed Hamiltonian 𝐻0
o 𝜓𝑛1 & 𝐸𝑛1 is unknown wavefunction and energy of Perturbed Hamiltonian which can be solved by First Order
correction.
o 𝜓𝑛2 & 𝐸𝑛2 is unknown wavefunction and energy of Perturbed Hamiltonian which can be solved by Second Order
correction.
o And so on.
 First Order correction (𝝍𝟏𝒏 & 𝑬𝟏𝒏 ):
First order correction 𝐸𝑛1 to the energy 𝐸𝑛 is the expectation value of perturbation 𝐻́ in unperturbed state 𝜓𝑛0 .
́ = ⟨𝜓𝑛0 |𝐻́ |𝜓𝑛0 ⟩ put in eq (2)
𝐸𝑛1 = 𝐻𝑛𝑛
𝑜𝑟
́
𝐸𝑛 = 𝐸𝑛0 + 𝐻𝑛𝑛
First order correction 𝜓𝑛1 to the wavefunction 𝜓𝑛 can be expressed as a linear combination of unperturbed state 𝜓𝑛0 .
(𝑛)
𝜓𝑛1 = ∑𝑚≠𝑛 𝑐𝑚 𝜓𝑚
2
𝑜𝑟
𝐻́𝑚𝑛 0 |𝐻́ |𝜓0 ⟩
⟨𝜓𝑚
𝜓𝑛1 = ∑𝑚≠𝑛 0 −𝐸 0 )
0 ∑
= 𝜓𝑚 𝑚≠𝑛
𝑛
0 −𝐸 0 )
0
𝜓𝑚 put in eq (2)
(𝐸𝑛 𝑚 (𝐸𝑛 𝑚
or
𝐻́𝑚𝑛
𝜓𝑛 = 𝜓𝑛0 + ∑ 0 0)
+
𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑚
These are the fundamental result of first order perturbation theory.
Second Order correction (𝝍𝟐𝒏 & 𝑬𝟐𝒏 ):
Second order correction 𝐸𝑛2 to the energy 𝐸𝑛 is

0 |𝐻́ |𝜓0 ⟩ 2
́ |2
|𝐻𝑚𝑛 ⟨𝜓𝑚 𝑛
𝐸𝑛2 = ∑𝑚≠𝑛 0 −𝐸 0 ) = ∑𝑖≠𝑛 0 −𝐸 0 ) put in eq (2)
(𝐸𝑛 𝑚 (𝐸𝑛 𝑚
𝑜𝑟
|𝐻́𝑚𝑛 |2
́ +∑
𝐸𝑛 = 𝐸𝑛0 + 𝐻𝑛𝑛 0 0
𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑚 )
Second order correction 𝜓𝑛2 to the wavefunction 𝜓𝑛 as,
1 ́ 𝐻𝑚𝑘
𝐻𝑘𝑛 ́ ́ 𝐻𝑚𝑛
𝐻𝑛𝑛 ́
𝜓𝑛2 = ∑ 0
[ 0
∑ 0 0 −∑ 0 0
0
] 𝜓𝑚
𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑚 ) 𝑘≠𝑛 (𝐸𝑛 − 𝐸𝑘 ) 𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑚 )
This is the fundamental result of second order perturbation theory.
Q. What is the Validity of the time-independent perturbation theory?
o ̂𝑝 = 𝜆𝐻̀ it produces must be small.

For perturbation theory to work, the corrections 𝐻
From second order correction 𝐸𝑛2 to the energy 𝐸𝑛 ;
𝐻́𝑚𝑛
𝐸𝑛2 = ∑ 0 0
𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑚 )
o If unperturbed states were equal or degenerate (i.e. 𝐸𝑛0 = 𝐸𝑚

0
share the same energy) then the condition would break
down. Then ordinary perturbation fails.
0 ́ 0 ́
⟨𝜓𝑚 |𝐻 |𝜓𝑛0 ⟩2 ⟨𝜓𝑚 |𝐻 |𝜓𝑛0 ⟩2
𝐸𝑛2 = ∑ 0 0
= ∑ = (𝑈𝑛𝑑𝑒𝑓𝑖𝑛𝑒𝑑)
𝑚≠𝑛 (𝐸𝑛 − 𝐸𝑛 ) 𝑚≠𝑛 0
 Time-Independent Degenerate Perturbation theory
̂0 . i.e In which two

The Time-Independent Perturbation Theory which has non-degenerate unperturbed Hamiltonian 𝐻
different unperturbed states shares the same energy.
Two fold degeneracy
Suppose the two solved SWE as

𝐻0 𝜓𝑎0 = 𝐸 0 𝜓𝑎0 , 𝐻0 𝜓𝑏0 = 𝐸 0 𝜓𝑏0
Now after perturbing we get
𝐻0 𝜓 0 = 𝐸 0 𝜓 0
Q. What is the need of the (time-independent) Degenerate perturbation theory?
 As we increases 𝜆 from 0 to 1, the perturbation 𝐻́ will break the degeneracy.

 Then the common unperturbed energy 𝐸 0 will split into two energy states as
1. Upper energy 𝐸+ state
2. Lower energy states 𝐸− .
 So now we have two unperturbed energy. i.e 𝐸 0 → 𝐸+ & 𝐸−
 Hence we cannot calculate first-order energy because we don’t know the single common
unperturbed energy
1
𝐸±1 = [𝑊𝑎𝑎 + 𝑊𝑏𝑏 ± √(𝑊𝑎𝑎 − 𝑊𝑏𝑏 )2 + 4|𝑊𝑎𝑏 |2 ]
2
These are the fundamental result of degenerate perturbation theory: the roots correspond to to perturbed energies. As
Upper perturbed energy 𝑬+ state

𝐸+1 = 𝑊𝑏𝑏 = ⟨𝜓𝑏0 |𝐻́ |𝜓𝑏0 ⟩
Lowet perturbed energy 𝑬+ state
𝐸_1 = 𝑊𝑎𝑎 = ⟨𝜓𝑎0 |𝐻́ |𝜓𝑎0 ⟩
1.52 What is Time-Dependent Perturbation theory?

The perturbation theory in which the Perturbation, Ĥ p = 𝜆𝐻́ , has explicit dependence on time H
̂p ≠ H ̂ p (t). And unperturbed
Hamiltonian, 𝐻0 , is time-independent.
Hamiltonians which can be split into two parts, a time-independent part 𝐻 ̂0 and a time-dependent part V(r) that is small compared
̂0
to 𝐻
̂ (𝑡) = 𝐻
𝐻 ̂0 + 𝑉̂ (𝑡)
Suppose particle start out in lower state

𝑐𝑎 (0) = 1, 𝑐𝑏 (0) = 0
 Quantum Statics: In which particle have only position
jh dependent potential 𝑉 = 𝑉(𝑟)
Zeroth Order (𝑪𝒂 (𝟎)& 𝑪𝒃 (𝟎)):  Quantum Dynamics: In which particle have both
position and time dependent potential 𝑉 = 𝑉(𝑟. 𝑡)
𝑐𝑎 (0) (𝑡) = 1, 𝑐𝑏 (0) (𝑡) = 0
First Order (𝑐𝑎 (1) (𝑡) & 𝑐𝑏 (1) (𝑡)):

𝑡
𝑖
𝑐𝑎 (1) (𝑡) = 1, ́ (𝑡̀)𝑒̀ 𝑖𝜔0𝑡̀ 𝑑𝑡̀
𝑐𝑏 (1) (𝑡) = − ∫ 𝐻𝑏𝑎
ℏ
0
Second Order (𝑐𝑎 (2) (𝑡) 𝑐𝑏 (2) (𝑡)):
𝑡 ̀ 𝑡
𝑖 𝑖 𝑖
𝑐𝑎 (2) (𝑡)
= − 𝑐𝑏 𝐻́𝑎𝑏 𝑒 −𝑖𝜔0 ̀
𝑡
= − ∫ 𝐻́𝑎𝑏 𝑒 0 (− ) ∫ 𝐻́𝑏𝑎 (𝑡̀̀)𝑒 𝑖𝜔0𝑡̀ 𝑑𝑡
−𝑖𝜔 ̀
𝑡
ℏ ℏ ℏ
0 0
(2) (𝑡)
𝑐𝑏 =0
1.53 What is Variational Principle?

The approximation method of finding the ground state energies is known as variation principle or Rayleigh–Ritz method
̂0 , then for solving such kind of problem by

When the system doesn’t have (closely related) solved unperturbed Hamiltonian 𝐻
special method known as Variation Principle.
The expectation value of Hamiltonian H in any state 𝜓 give the approximation value of ground-state energy.
𝐸𝑔 ≤ 〈𝜓|𝐻|𝜓〉
The mathematical expression is given as,
𝐸𝑔 ≤ 〈𝜓|𝐻|𝜓〉 ≡ 〈𝐻〉
Where We can express 𝝍 as the linear combination of unknown

𝝍′𝒔 of Hamiltonian H
𝐸𝑔 is the ground state energy ∞
𝝍 = ∑ 𝑪𝒏 𝝍𝒏 = 𝒄𝟏 𝝍𝟏 + 𝒄𝟐 𝝍𝟐 +. . . . . ..
𝒊=𝟏
Ground state energy 〈𝑯〉 of Harmonic oscillator (1-Dimension) is
ℏ𝜔
〈𝐻〉 ≡
2
̂ 〉 of Hydrogen atom is
Also ground state energy 〈𝑯
𝑚𝑒 2
〈𝐻〉 ≡ −
2ℏ
Let A be Hermitian operator and commutes with the H. Then 𝝍𝟎𝒂 and 𝝍𝟎𝒃 are the
Eigenfunctions of H wit the different Eigenvalues
𝑨𝝍𝟎𝒂 = 𝝁𝝍𝟎𝒂 , 𝑨𝝍𝟎𝒃 = 𝝊𝝍𝟎𝒃 𝒂𝒏𝒅 𝝁 ≠ 𝝊 𝒕𝒉𝒆𝒏 𝑾𝒂𝒃 = 𝟎
〈𝝍𝟎𝒂 𝑯|𝝍́ 𝟎〉 = 𝟎
𝒃
1.54 What is WKB Approximation?

WKB Approximation is the techniques for obtaining approximate solution to the time independent Schrodinger equation to
calculating the bound state energies and the tunneling rate through the potential.
WKB approximation seek the solution only to the time independent Schrodinger equation which are valid in the near class-
classical domain where potential 𝑉 varies slowly.
The Wetzel–Kramer’s–Brillouin (WKB) method is useful for approximate the solution of systems with slowly varying potentials
where potentials which remain almost constant over a region of the order of the de Broglie wavelength.. The WKB method can
thus be viewed as a semiclassical approximation.
The mathematical expression can be written as,
𝐶 𝑖
𝜓± (𝑥) ≅ 𝑒 ±ℏ ∫ 𝑝(𝑥)𝑑𝑥
√𝑝(𝑥)
𝑜𝑟
𝐶+ 𝑖 𝐶− 𝑖
𝜓+ (𝑥) ≅ 𝑒 ℏ ∫ 𝑝(𝑥)𝑑𝑥 , 𝜓− (𝑥) ≅ 𝑒 −ℏ ∫ 𝑝(𝑥)𝑑𝑥
√𝑝(𝑥) √𝑝(𝑥)
1
The probability of finding the particle is proportional to momentum 𝑝(𝑥).i.e (|𝜓(𝑥)|2 ∝ ).This is what we expect for
√𝑝(𝑥)
a “classical” particle because the time it will take to travel a distance dx is proportional to the inverse of its speed (or its
momentum)i.e (𝑑𝑥 = 𝑣𝑡 → 𝑡 = 𝑑𝑥/𝑣 or 𝑡 ∝ 1/𝑣 )
 Case – 1: 𝑬 > 𝑽(𝒙) or (Classically allowed region)
When particle all having energy E is greater than potential 𝑽(𝒙)

 Classically, the particles approach the potential step or barrier 𝑉(𝑥) . None of the particles get reflected. So there will be
total transmission.
 But Quantum mechanics says that even particles has sufficient energy E higher than potential step 𝑉(𝑥) then it is possible
that there will be reflection through potential 𝑉(𝑥)
The general solution will be given as
𝐶+ 𝑖 𝐶− 𝑖
𝜓(𝑥) = 𝑒 ℏ ∫ 𝑝(𝑥)𝑑𝑥 + 𝑒 −ℏ ∫ 𝑝(𝑥)𝑑𝑥
√𝑝(𝑥) √𝑝(𝑥)
 Case – 2: 𝑬 < 𝑽(𝒙) (Tunneling )or (Classically Forbidden region)

When particle all E is smaller than potential step 𝑉(𝑥).
 Classically, the particles arriving at potential step or barrier 𝑉0 from the left will come to a stop. None of the particles will
make it into the right side of the barrier there is total reflection of the particles
 But Quantum mechanically there is a non-zero probability that the wave function penetrates this potential step or barrier 𝑉0 .
The quantum mechanical effect which is due to the wave aspect of microscopic objects can tunnel through classically
impenetrable barriers known as the tunneling effect
𝐶− 1 𝐶+ 1
𝜓(𝑥) = 𝑒 −ℏ ∫ 𝑝(𝑥)𝑑𝑥 + 𝑒 +ℏ ∫ 𝑝(𝑥)𝑑𝑥
√𝑝(𝑥) √𝑝(𝑥)
 Case – 3: 𝑬 ≅ 𝑽(𝒙) (Tunneling )or (Classica; Turning points or Tunnelling region)

When particle all E is nearly equal to potential step 𝑉(𝑥).
 Classically, the particles arriving at potential step or barrier 𝑉0 will come to a stop. Hence
1
momentum vanishes 𝑝(𝑥) = 0 and wavefunction become infinite. (i.e. since |𝜓(𝑥)|2 ∝ ).
√𝑝(𝑥)
So the WKB approximation is valid in both the classical allowed and forbidden regions but not
at the classical turning points.
 But Quantum mechanically, however, the probability corresponding to the particle’s tunneling through the barrier and
“emerging” of the barrier is not zero. In what follows we want to use the WKB approximation to estimate the particle’s
probability of passing through the barrier. 𝑉(𝑥)
𝐶 1
𝜓(𝑥) = 𝑒 −ℏ ∫ 𝑝(𝑥)𝑑𝑥
√𝑝(𝑥)
The probability corresponding to the particle’s passage through the barrier is given by the transmission coefficient
|𝐸|2
𝑇= = 𝑒 −2𝛾
|𝐴|2
Q. What is the validity or condition of WKB method?
Classically, the particles arriving at potential s 𝑉(𝑥) will come to a stop. Hence momentum vanishes 𝑝(𝑥) = 0 and
1
wavefunction become infinite. (i.e. since |𝜓(𝑥)|2 ∝ ). So the WKB approximation is valid in both the classical allowed
√𝑝(𝑥)
and forbidden regions but not at the classical turning points.
Also the condition of validity for the WKB method is given by
Q. What is the cold emission?
When a metal is subject to an external electric field, electrons can be emitted from the metal. This is known as cold emission
Galilean Relativity: Galilean invariance or Galilean relativity states that the laws of
motion are the same in all inertial frame
1. There exists an absolute space, in which Newton's laws are true.

2. All inertial frames have a universal or constant time.
1.55 What’s so special in Special theory of Relativity?

Relativity,
 It is the the field of science that measures events where and when they happen,
and by how much any two events are separated in space and in time.
 It has to do with transforming of measurements (energy and
momentum) between reference frames that move relative to each other.
 Relativity connects space and time, matter and energy, electricity
and magnetism
 History
As the nineteenth century turned to the twentieth, however, a major revolution comes to the world of physics.
 In 1900 Planck provided the basic ideas that led to the formulation of the Quantum Mechanics,
 In 1905 at the age of only 26 Albert Einstein formulated his brilliant special theory of relativity.
(The adjective special means that the theory deals only with inertial reference frames, which are frames in which
Newton’s laws are valid.)
Special theory of relativity:
Branch of modern physics that deal with the observation of objects moving with the
speed v approaching to speed of light c.(i.e. v = c = 3 × 108 𝑚𝑠 −1 ).
Before going to postulates of special theory of relativity, first we have to study few
very important terms as follows
1. Relative motion
An object is said to be in relative motion when it is changing its position with

respect to its reference.(any initial point)
Examples
 Wall of the cabin of a moving train are in relative motion to a person at rest on ground
 Since Earth is orbiting with orbital velocity of 30𝑚𝑠 −1 around Sun. So Earth and Observer (you) will
always be in relative motion.
(So there is no complete rest, in universe everything is in motion.)
All Motion are Relative:
Motion and rest are described with respect to some reference, thus we cannot say whether an object is absolutely at
rest or absolutely at motion.
So there is no such terms as Absolute (complete) rest or Absolute (complete) motion.
2. Frame of reference
Any co-ordinate system relative to which measurements of (rest and motion) are taken.
Examples
 Walls of room
 College library
 Mosque e.t.c
Types of Frame of Refrence:
1. Inertial Frame of Reference
o A type of frame of reference which is either at rest or moving with uniform velocity.
o It is also called Non-accelerated frame of reference.
o All the Newton’s law of motion are valid in this frame of reference.
o A car moving with uniform velocity and classroom at rest is example of inertial frame of reference.
2. Non-inertial Frame of reference
o A type of frame of reference which is moving with non-uniform velocity.

o It is also called Accelerated frame of reference.
o All the Newton’s law of motion are not valid in this frame of reference.
o A car or train moving with non-uniform velocity are example of Non-inertial frame of reference.
Postulates of Special theory of relativity:

There are two basics postulates of special theory of relativity as,
(i) The Relativity Postulate: The Laws of physics are same in all Inertial frame of reference.
Or
(The laws of physics are the same for observers in all inertial reference frames. No one frame is preferred over any
other.)
(ii) The Speed of Light Postulate The speed of light in free space is a universal constant i.e. 3 × 108 𝑚𝑠 −1 which is
independent on speed of source.
Or
(The speed of light in vacuum has the same values (c=299 792 458 m/s) in all directions and in all inertial
reference frames)
Result of Special theory of Relativity: The Ultimate Speed:

Speed of light 𝒄 = 𝟐𝟗𝟗, 𝟕𝟗𝟐, 𝟒𝟓𝟖 𝒎𝒔−𝟏
 Time Dilation
A moving clock ticks more slowly than a clock at rest

Time is not absolute its depends on motion of frame of reference. It increases according to formula as
𝑡0
𝑡=
2
√1 − 𝑣2
𝑐
Where
𝑡 is relativistic time i.e measured with relative motion
𝑡0 is proper time i.e measured with rest state
𝑣 is speed of relative motion
𝑐 is speed of light
𝑣
√1 − 𝑐 is always less then 1
𝑡0
So 𝑡 = 𝑡ℎ𝑒𝑛 𝑡 > 𝑡0 ,
1
 Length Contracion
Faster means shorter

Length measures along the motion appear to be decreases according to the relation as,
𝑣2
𝐿 = 𝐿0 √1 −
𝑐2
Where
𝐿 is relativistic length i.e measured with relative motion
𝐿0 is proper length i.e measured with rest state
𝑣
So 𝐿 = 𝐿0 (1) 𝑡ℎ𝑒𝑛 𝐿 < 𝐿0
 Mass variation
Greater speed infinite mass

Mass of the object is varying quantity and it appear to be increases as object moves according to relation as
𝑚0
𝑚= 𝑣
—(1)
√1−
𝑐
Where
𝑚 is relativistic mass i.e measured with relative motion
𝑚0 is proper mass i.e measured with rest state
𝑣
𝑚0
So 𝑚 = 𝑡ℎ𝑒𝑛 𝑚 > 𝑚0
1
According to equation (1) the speed of light cannot be achieved by any object other than photon. Because
as speed of object v increases up to speed of light c then (v=c) which makes denominator in eq. (1) zero
and which lead to mass to infinite 𝑚 → ∞ which is impossible.
𝑚0 𝑚0 𝑚0
𝑚= = = = ∞(𝑢𝑛𝑑𝑒𝑓𝑖𝑛𝑒𝑑)
𝑐2 √1 − 1 √𝑜
√1 −
𝑐2
 Invalidity of relativity in everyday life

Time, mass and length remain unchanged during everyday life because velocity of object v is very small as
compared to speed of light in daily life.
so
𝑡0 𝑡0
𝑡= = = 𝑡0
𝑣2 1
√1 −
𝑐2
𝑣2
𝐿 = 𝐿0 √1 − = 𝐿0 (1) = 𝐿0
𝑐2
𝑚0 𝑚
𝑚= = =𝑚
𝑣2 1
√1 −
𝑐2
 Energy mass reation
Law of conservation of mass and energy

According to Einstein enery and mass are two different quantities but are interconvert able by a realtion as
𝐸 = 𝑚𝑐 2
Relativistic Linear Momentum
The relativistic value calculated for the linear momentum p of a particle must
approach the classical value m𝑣 as 𝑣 approaches zero.
𝑚𝑣
𝑝=
2
√1 − 𝑣2
𝑐
Relativistic Energy
𝑚𝑐 2
𝐸=
2
√1 − 𝑣2
𝑐
Where
𝐸 is relativistic energy i.e measured with relative motion
𝐸0 is proper or rest energy i.e measured with rest state
𝑣
When the particle is at rest it energy will be rest energy 𝑬𝟎 = 𝑚𝑐 2
Energy–momentum relationship for a relativistic particle 𝐸 = √𝑝2 𝑐 2 + (𝑚𝑐 2 )2

Consequences of Special theory of Relativity: (optional)
 Twin paradox.
An intriguing consequence of time dilation is the so-called twin paradox.
 The non-symmetric aging of the twins has been verified by experiments in which accurate clocks were
taken on an airplane trip around the world and then compared with identical clocks that had been left
behind. An observer who departs from an inertial system and then returns after moving relative to that
system will always find his or her clocks slow compared with clocks that stayed in the system.
 So Speedo is younger than Goslo because Speedo’s clock in his rocket run slower than Goslo’s clock on
Earth.
Application of Special theory of Relativity:

Navstar navigation system:
 It is a modern system of navigation of satellite capable to find the position and speed of any object on earth
up to an accuracy of about 2 cm/s
 It uses the principle of special theory of Relativity.
Galilean Relativity: Galilean invariance or Galilean relativity states that the laws of The SWE do not describe the spin nature of
motion are the same in all inertial frame particle
The SWE doesn’t not provide any
information about high energy phenomena
3. There exists an absolute space, in which Newton's laws are true.
like pair production
4. All inertial frames have a universal or constant time.
1.56 Differentiate between Non-Relativistics & Relativistics QM?
Non-Relativistic Quantum Mechanics:

Non-relativistic quantum mechanics refers to the mathematical formulation of quantum mechanics applied in the context of
Galilean relativity.
The Schrödinger Equation only describes particles in the non-relativistic limit (𝑣 ≪ 𝑐).
To describe the particles at particle colliders we need to incorporate special relativity.
 The quantum mechanics based on Schrodinger wave equation is known as Non-Relativistic Quantum Mechanics.
 It deal with the motion of particles whose velocities is much lesser than the velocity of light (𝑣 ≪ 𝑐).
 It doesn’t deal with the spin nature of particle.
Relativistic Quantum Mechanics:

Making the Schrödinger equation relativistic
Relativistic quantum mechanics is applicable to massive particles propagating at all velocities up to those comparable to the
speed of light c, or massless particles.
Relativistic quantum mechanics is quantum mechanics applied with special relativity
 The branch of quantum mechanics which deals with the motion of the particle that have speed approaching to the speed
of light.
 The superposition principle should hold therefore equation of motion must be linear
 Equation of motion must be invariant under the Lorentz transformation.
Application
The theory has application in
o high energy physics
o Particle physics
o Accelerator physics,
o Atomic physics,
o Chemistry
o Condensed matter physics.
Key features
o the prediction of antimatter,
o spin magnetic moments of elementary spin 1/2 fermions,
o fine structure,
o quantum dynamics of charged particles in electromagnetic fields
o Dirac equation
o Klein Garden equation or Relativistic equation
Relativistic Linear Momentum
𝑚𝑣
𝑝=
2
√1 − 𝑣2
𝑐
Where
𝑝 is relativistic energy i.e measured with relative motion
𝑝0 = 𝑚𝑣 is proper or rest energy i.e measured with rest state
𝑣
Relativistic Energy
𝑚𝑐 2
𝐸=
2
√1 − 𝑣2
𝑐
Where
𝐸 is relativistic energy i.e measured with relative motion
𝐸0 = 𝑚𝑐 2 is proper or rest energy i.e measured with rest state
𝑣
When the particle is at rest it energy will be rest energy 𝑬𝟎 = 𝑚𝑐 2
Energy–momentum relationship for a relativistic particle 𝐸 = √𝑝2 𝑐 2 + (𝑚𝑐 2 )2

1.57 What is Klein Garden equation?

The equation was named after the physicists Oskar Klein and Walter Gordon, who in 1926 proposed that it describes relativistic
electrons. It is also called Relativistic wave equation.
It is Relativistic correction of Schrödinger wave equation.

It describe the dynamics of spin less relativistic composite particles (i.e pion and Higgs boson)
This is the relativistic wave equation for a spin zero particle.
Mathematical representation of Klein Garden equation is given as,
𝜕2
(𝑚2 𝑐 4 − ℏ2 𝑐 2 ∇2 )Ψ(𝑟, 𝑡) == ℏ2 Ψ(𝑟, 𝑡)
𝜕2𝑥
Solution or wavefuction of Klein Garden equation or Relativistic wave equation is given as
𝐸𝑡
Ψ(𝑟, 𝑡) = 𝑈𝑒 −𝑖( ℏ −𝑘.𝑟)
Which lead to the energy expression as,
𝐸 = ±√𝑚2 𝑐 4 − ℏ2 𝑐 2 𝑘 2
So instead of single positive solution it has both negative and positive solution.
This is why Schrödinger abandoned this equation

and developed the nonrelativistic Schrödinger
equation instead – he (implicitly) took the positive
sign of the square root so that he could ignore the
negative energy solutions.
Feynman-Stuckelberg Interpretation
Feynman and Stuckelberg suggested that negative
energy states propagate backwards in time
Drawbacks
 In quantum mechanics energy doesn’t decrease from ground state but Klein Garden equation with negative value violate
this axiom.
 Negative energy states have negative probability distributions 𝜌(𝑟, 𝑡) which is not possible.
𝜕𝜌(𝑟,𝑡)
+ ∇. 𝑈(𝑟, 𝑡) = 0 ------ Equation of continuity.
𝜕𝑥
 It describe only spin less particle
 It do not give any explanation about fine structure of hydrogen atom
Expression of probability density 𝝆(𝒓, 𝒕)& Equation of continuity 𝑱(𝒓, 𝒕).
𝑖ℏ 𝜕 𝜕
𝜌(𝑟, 𝑡) = [Ψ ∗ (𝑟, 𝑡) Ψ(𝑟, 𝑡) − Ψ(𝑟, 𝑡) Ψ ∗ (𝑟, 𝑡)]
2𝑚𝑐 2 𝜕𝑡 𝜕𝑡
ℏ
𝐽(𝑟, 𝑡) = [Ψ ∗ (𝑟, 𝑡)∇Ψ(𝑟, 𝑡) − Ψ(𝑟, 𝑡)∇Ψ ∗ (𝑟, 𝑡)]
2𝑖𝑚
Relativistic invariance of Klein Garden equation
 Position operator in the relativistic mechanics
𝑋̂ = (𝑥1 , 𝑥2 , 𝑥3 , 𝑖𝑐𝑡)
 Momentum operator in the relativistic mechanics
𝑝̂ = (𝑝1 , 𝑝2 , 𝑝3 , 𝑖𝑐𝑡)
𝜕 𝜕 𝜕 𝑖𝐸
𝑝̂ = (−𝑖ℏ , −𝑖ℏ , −𝑖ℏ , )
𝜕𝑥 𝜕𝑦 𝜕𝑧 𝑐
 Current density four vectors
𝐽̂ = (𝐽1 , 𝐽2 , 𝐽3 , 𝑖𝑐𝜌)
 Vector potential four vectors
𝐴̂ = (𝐴1 , 𝐴2 , 𝐴3 , 𝑖𝜙)
 Wave vector
𝑖𝜔
̂ = (𝑘,
𝐾 )
𝑐
1.58 What is Dirac Equation?

In 1928 British physicist Paul Dirac derived the Dirac equation called is a relativistic wave equation. It describes all spin-1/2
massive particles such as electrons and quarks. The equation also implied the existence of a new form of matter, antimatter (i.e
positron)
It is Relativistic plus Spin correction of Schrödinger wave equation

It describe the dynamics of spin (+1/2 , -1/2) relativistic composite particles (i.e electrons and quarks)
This is the relativistic wave equation for a Non-zeros pin zero particle.
The problems with the Klein-Gordon equation all came about because of the square root required to get the energy.
𝐸 = ±√𝑚2 𝑐 4 − ℏ2 𝑐 2 𝑘 2
The Dirac equation in the form originally proposed by Dirac is
Covariant form and relativistic invariance
In practice one often writes the gamma matrices in terms of 2 × 2 sub-matrices taken from the Pauli matrices and the 2 × 2
identity matrix. Explicitly the standard representation is
1.59 Problems
Q.1 Prove that Eigen value of Hermitian operator are real.
Q.2

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Quantum Mechanics (Revised Edition) 1

Ψ Notes Compiled from

1.0 What is Quantum Mechanics?

1.0 What is Quantum Mechanics?

The word Quantum derives from

1.1 Origin of Quantum Mechanics

1.2 Contribution of scientists

Albert Einstein ____ The Photoelectric Effect

 In 1905 Einstein confirmed the Planck’s quantum concept.

Niels Bohr ___ The model of Hydrogen atom

Arther Holy Compton ____ Compton’s effect

de Broglie ___ Matter is a wave and wave is a matter too!

 In 1923, de Broglie proposed that Matter waves.

Heisenberg___ The Uncertainty principle ( One thing at a Time!)

Erwin Schrödinger___ The Schrodinger Wave Equation of Particle (SWE)

Paul Dirac___ An easy <Bra|Ket> Notation of wavefunction 𝜳 and Relativistic approaches

1.31 What is a Wavefunction 𝚿(𝒓, 𝒕)?

Orthognality: (Condition of orthognality)

Orthonormalization: (Condition of Normalization + othognalization)

Where 𝛿𝑚𝑛 is Knocker delta function given as,

Q Why normalization is necessary?

𝐴̂Ψ = 𝑎Ψ ́ ____Eigenvalue Equation Eigen Value Equation is

Q. What is linear operator?

 Identity Operator 𝑰̂: Which leave the wavefunction unchanged

 Parity Operator or Inversion Operator 𝓟 ̂:

𝒫̂ 𝜓(𝑟) = 𝒫̂ 𝜓(−𝑟) and 𝒫̂ 2 = 1 𝑜𝑟 𝒫̂ = 𝒫̂ −1

 Exchange Operator or Permutation Operator 𝑷 ̂ 𝒊𝒋:

 Orbital Angular Momentum Operator 𝑳̂:

1.33 What is a Schrödinger Wave Equation?

To solve SWE we assume the separable solution of wavefunction as

In Time Independent Schrödinger Wave Equation

Time Independent Schrödinger Wave Equation is

Time Dependent Schrödinger Wave Equation is

The Linear Vector Space

1.34 What is Hilbert Space 𝓗?

1.35 What is Dirac Notation?

Properties of Kets, Bras and Bra-kets.

1.7 Define Postulates of Quantum Mechanics?

1. Postulate-1:Wavefunction or state of system 𝜳(𝒓, 𝒕):

2. Postulate-2:Observable and Operator:

̂ ): is a mathematical rule when applied on wavefunction Ψ transform it to another wavefunction Ψ́ (eigenfuction)

𝐴̂Ψ = 𝑎Ψ ́ ____Eigenvalue Equation

Eigen is a German word means

3. Postulate-3: Eigenvalues of operators or Measurements of Operator:

𝐴̂Ψ = 𝑎𝑛 Ψ ́ _____ Eigen Value Equation

Q. What is the Eigen value of Hermitian operator?

4. Postulate-4: Expectation value or Probabilistic outcome of measurements:

e.g Hamiltonian is the Expectation value of Energy operator 𝐸̂ =< Ψ|𝐻

5. Postulate-5: Time Evolution of system

1.36 What is Commutation Relation?

Important Commutation Relation:

(i) [𝑥̂, 𝑝̂𝑥 ] = −𝑖ℏ

[𝑝̂𝑥 , 𝑥̂] = [𝑝̂𝑦 , 𝑦̂] = [𝑝̂𝑧 , 𝑧̂] = −𝑖ℏ

(ii) [𝑥̂, 𝑝̂𝑦 ] = 0

2. Orbital Angular momentum commutation L:

(i) [𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ℏ𝐿̂𝑧

[𝐿̂𝑧 , 𝐿̂𝑦 ] = −𝑖ℏ𝐿̂𝑥

3. ̂ and Orbital angular Momentum 𝑳̂ :

(ii) [𝑥̂, 𝐿̂𝑦 ] = 𝑖ℏ𝑧̂

4. Linear and Orbital angular Momentum 𝑷 ̂ & 𝑳̂ :

(i) [𝑦, 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑧 − 𝑧𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]

[𝑝𝑦 , 𝐿2 ] = 𝑖ℏ[−𝐿𝑥 𝑝𝑧 − 𝑝𝑧 𝐿𝑥 + 𝐿𝑧 𝑥 + 𝑥𝐿𝑧 ]

7. Lowering and Raising Operators 𝑳̂+ & 𝑳̂− :