QUANTUM MECHANICS

Quantum Mechanics is a branch of mechanics that deals with the mathematical description of the motion
and interaction of subatomic particles. It incorporates the concepts of quantization of energy, wave–particle
duality and the uncertainty principle.
Matter Waves
Waves associated with a particle in motion are called de Broglie waves. In case of photons, energy can be
expressed as
𝑐
𝐸 = ℎ𝜐 = ℎ 𝜆 (wave nature)
𝐸 = 𝑚𝑐 2 (Particle nature)
2 𝑐
𝑚𝑐 = ℎ𝜆 (wave- particle dual nature)
ℎ
𝑚𝑐 = 𝜆
ℎ
de Broglie wavelength 𝜆 = 𝑝
In general, for a particle of mass ‘m’ and velocity ‘v’, the associated matter wave is of wavelength
ℎ ℎ ℎ ℎ
𝜆= = = =
𝑝 𝑚𝑣 √2𝑚𝐾𝐸 √2𝑚 𝑒𝑉
For an electron accelerated through a potential ‘V’, the associated matter wave is of wavelength
150
𝜆=√ 𝑉
Å

Wave function (Ψ)

In a wave there is something that varies periodically. In case of electromagnetic waves, the electric
and magnetic fields vary periodically, whereas in sound waves, pressure varies periodically. In water
waves the height of water surface varies periodically. Similarly in matter waves, a quantity that varies
is called wave function, denoted by Ψ. It is a mathematical function in terms of position and time that
represent state of a particle.
Wave function Ψ is a complex quantity, which gives ‘the idea of the probability of finding the particle’
in a particular region of space.
Properties / Physical Significance of Wave Function (Ψ)
1. The wave function Ψ is complex quantity, so one can not measure it.
2. The wave function relates the particle nature and wave nature statistically.
3. Square of the wave function ΨΨ* = |ψ| 2 is a real quantity and gives the probability of finding a
particle in region of space.
Position probability density, 𝑃 = ∫|𝛹 2 | 𝑑𝜏
Value of P is between 0 and 1. For ex; if P=0.4, it means there is a 40% chance for the presence of
particle.
4. It does not predict the exact location of the particle, but it says where the particle is likely to be.
Normalization of Wave function
A wave function, which satisfies equation∫|𝛹 2 | 𝑑𝜏 = 1 is said to be normalized to unity or simply
normalized. This means particle which exist in a particular region must be found somewhere in that
region, i.e., the probability of finding the particle in that region will be 100%, i.e., unity.
Wave function of a particle with energy E and momentum p
Consider a particle moving in x-direction with momentum ‘p’. The wave function of the particle can
be written in the form
𝛹 = 𝑎𝑒 −𝑖[𝜔𝑡−𝑘𝑥] ------------------------------------------------------------------------------------(1)

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 2𝜋 2𝜋
where ‘a’ is the amplitude ,𝜔 = 𝑇
and𝑘 = 𝜆
2𝜋 2𝜋ℎ𝜈 2𝜋 𝐸
𝜔= 𝑇
= 2𝜋𝜈 = ℎ
= ℎ
𝐸 = ℏ
-------------------------------------------------------------(2)
ℎ
where E-energy of particle and ℏ = 2𝜋

Using de Broglie wave equation,

2𝜋 2𝜋𝑝 𝑝
𝑘= = = ---------------------------------------------------------------------------------(3)
𝜆 ℎ ℏ

Using eqn (2) and (3)in (1)

−𝑖
[𝐸𝑡−𝑝𝑥]
𝛹 = 𝑎𝑒 ℏ
TIME-DEPENDENT SCHRÖDINGER EQUATION
Consider a particle moving in x-direction with momentum ‘p’. wave function of the particle is
−𝑖
[𝐸𝑡−𝑝𝑥]
𝛹 = 𝑎𝑒 ℏ ------------------------------------------------------------------------------------(1)
Differentiating (1) w.r.t. ‘t’
𝜕𝛹 −𝑖 −𝑖
[𝐸𝑡−𝑝𝑥]
= 𝐸𝑎𝑒 ℏ
𝜕𝑡 ℏ
𝜕𝛹 −𝑖
𝜕𝑡
= ℏ
𝐸𝛹 using eqn (1)
𝜕𝛹
𝐸𝛹 = 𝑖ℏ 𝜕𝑡
--------------------------------------------------------------------------------------(2)
Differentiating (1) w.r.t. ‘x’ twice
𝜕2𝛹 𝑖 𝑖 −𝑖
[𝐸𝑡−𝑝𝑥]
2
= 𝑝 𝑝 𝑎𝑒 ℏ
𝜕𝑥 ℏ ℏ
𝜕2 𝛹 −𝑝2
= 𝛹using equation (1)
𝜕𝑥 2 ℏ2
𝜕2 𝛹
𝑝2 𝛹 = −ℏ2 𝜕𝑥 2 -----------------------------------------------------------------------------------(3)
Total energy of the particle is the sum of KE and PE
𝑝2
𝐸= +𝑉
2𝑚
Multiplying by ψ
𝑝2
𝐸𝛹 = 𝛹 + 𝑉𝛹
2𝑚
Using eqns (2) and (3)
𝝏𝜳 −ℏ𝟐 𝝏𝟐 𝜳
𝒊ℏ = + 𝑽𝜳 -----------------------------------------------------------------------------(4)
𝝏𝒕 𝟐𝒎 𝝏𝒙𝟐
This is the time dependent Schrodinger equation in one dimension. In 3dimension,
𝜕𝛹 −ℏ2 2
𝑖ℏ = 𝛻 𝛹 + 𝑉𝛹
𝜕𝑡 2𝑚
where 𝛻 2 is the Laplacian operator
TIME INDEPENDENT SCHRÖDINGER EQUATION
In many cases the potential (V) is independent of time and depends only on position. In such steady
state cases, the Schrodinger equation can be simplified by separating the time dependent and
independent parts.
Wave function of a particle moving in x-direction with momentum ‘p’ is

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 −𝑖
[𝐸𝑡−𝑝𝑥]
𝛹 = 𝑎𝑒 ℏ
−𝑖 𝑖
𝐸𝑡 𝑝𝑥
𝛹 = 𝑎𝑒 ℏ 𝑒ℏ
−𝑖
𝛹 = 𝛹𝑜 𝑒 ℏ 𝐸𝑡 ----------------------------------------------------------------------------------------(1)
where 𝛹𝑜 is a function that depend on position only
Differentiating eqn (1) w.r.t. ‘t’
−𝑖
𝜕𝛹 −𝑖 𝐸𝑡
𝜕𝑡
= ℏ
𝐸𝛹𝑜 𝑒 ℏ --------------------------------------------------------------------------------------(2)

Differentiating eqn (1) w.r.t. ‘x’ twice

−𝑖
𝜕2 𝛹 𝜕2 𝛹𝑜
= 𝑒 ℏ 𝐸𝑡 ------------------------------------------------------------------------------------(3)
𝜕𝑥 2 𝜕𝑥 2
The time dependent Schrodinger equation is
𝜕𝛹 −ℏ2 𝜕2 𝛹
𝑖ℏ 𝜕𝑡 = + 𝑉𝛹 -----------------------------------------------------------------------------(4)
2𝑚 𝜕𝑥 2
Using (1), (2) and (3) in (4)
−𝑖 −𝑖 −ℏ2 𝜕 2 𝛹𝑜 −𝑖𝐸𝑡 −𝑖
𝑖ℏ 𝐸𝛹𝑜 𝑒 ℏ 𝐸𝑡 = 𝑒 ℏ + 𝑉𝛹 𝑜 𝑒 ℏ
𝐸𝑡
ℏ 2𝑚 𝜕𝑥 2
−𝑖 −ℏ2 𝜕 2 𝛹𝑜 −𝑖𝐸𝑡 −𝑖
𝐸𝛹𝑜 𝑒 ℏ 𝐸𝑡 = 𝑒 ℏ + 𝑉𝛹 𝑒
𝑜 ℏ
𝐸𝑡
2𝑚 𝜕𝑥 2
−ℏ2 𝜕 2 𝛹𝑜
𝐸𝛹𝑜 = + 𝑉𝛹𝑜
2𝑚 𝜕𝑥 2
ℏ𝟐 𝝏𝟐 𝜳𝒐
+ (𝑬 − 𝑽)𝜳𝒐 = 𝟎-------------------------------------------------------------------------(5)
𝟐𝒎 𝝏𝒙𝟐
This is the time independent Schrodinger equation in one dimension. In three dimensions it takes
the form
ℏ2 2
𝛻 𝛹𝑜 + (𝐸 − 𝑉)𝛹𝑜 = 0
2𝑚
ONE DIMENSIONAL INFINITE SQUARE WELL POTENTIAL (PARTICLE IN A ONE-
DIMENSIONAL BOX)
Consider a particle of mass ’m’ confined in an infinite square well potential of width L defined by
V=0 for x>0 to x<L and
V
V=∞ for x⋜0and x⋝L
Time independent Schrodinger equation V= V=
of the particle in the region II (where
V=0) is I II III
ℏ2 ∂2 Ψ
+ (E − 0)Ψ = 0
2m ∂x 2
∂2 Ψ 2m V=0
+ 2 EΨ = 0 x
∂x 2 ℏ 0 L
∂2 Ψ
+ k2Ψ = 0 ---------------------(1)
∂x2

2mE
where k = √ ----------------------(2)
ℏ2

Possible solution of eqn (1) is

Ψ = A cos(kx) + sin(kx) ----------------------------------------------------------------------------------(3)

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Probability of finding the particle outside the well is zero. So Ѱ*Ѱ must be zero at walls (at x=0 and
x=L). This means Ѱ must be zero at walls.
Applying boundary condition; at x=0, Ѱ(x) =0
Ѱ(0)= Acos(k. 0) + Bsin(k. 0)=0
This is valid only if A=0
∴ Ψ = Bsin(kx)
Applying boundary condition;, at x=L , Ѱ(x)=0
Ѱ(L)= Bsin(kL) = 0
This is valid only when kL=nπ
nπ
k= ----------------------------------------------------------------------------------------------------(4)
L
nπ
∴ Ψn = Bsin ( x)
L
2
By using the normalization condition and applying limits it can be shown that B = √L

----------------------------------------------------------------------------------------(5)
𝟐 𝐧𝛑
𝚿𝐧 = √ 𝐬𝐢𝐧 ( 𝐱) where n=1,2,3 ……
𝐋 𝐋

n=0 is not admissible because when n=0, Ψ(x) =0 inside the box which means particle is not present
inside the box.
Wave function and probability of finding the particle are represented below figure.

Wave function Ψn(x) Position Probability Ψn2(x)

n=3 Ψ3 ІΨ3І2

n=2 Ψ2 ІΨ2І2

n=1 Ψ1 ІΨ1І2
x=0 0.25L 0.5L 0.75L L x=0 0.25L 0.5L 0.75L L
𝐱 𝐧𝛑
(Note: when x varies from 0 to L , varies from0 to L and 𝐱 varies from0 to nπ)
𝐋 𝐋
In ground state (n=1) maximum probability of finding the particle is at the midpoint. But for n=2,
the maximum probabilities are at ¼ th and ¾ th distance from one end of the box.
Allowed Energy Levels
From (2) and (4)
n2 π2 2mE
= 2
L2 ℏ
n 2 π2 ℏ 2 n2 h2
En = or En = 8mL2 (using ℏ=h/2π)
2mL2

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 h2
when n=1, E1 =
8mL2
4 h2
when n=2, E2 =
8mL2
9 h2
when n=3, E3 =
8mL2
This means that particle cannot have any arbitrary energy value but can
have only certain discrete values. Also the particle cannot have zero
energy.
h2
E1 = 8mL2 for n=1 is the minimum energy a particle can have and is
called zero point energy
The number ‘n’ is the quantum number.
Thus confinement of particle in a potential well leads to;
i. Certain preferred positions of maximum probability of finding the particle.
ii. Particle is allowed to have certain discrete energy levels only.
iii. There is a minimum limit to the energy that particle can have.
Quantum Mechanical Tunneling
According to classical mechanics, when a particle of lower kinetic energy approaches a larger
potential barrier (E<V0), it bounces off. But in quantum mechanics the wave function representing
the particle does not vanish on the other side of the barrier. This means there is a finite probability
of particle penetrating the barrier exists. Phenomenon of penetration of particle through barriers
higher than their own energy is known as quantum
mechanical tunnelling.
Wave function of the incident and transmitted particle
are
𝛹1 = 𝐴𝑒 ikx + 𝐵𝑒 −ikx
Where A represent the amplitude of incident wave and
B represent the amplitude of reflected wave.
𝛹3 = 𝐹𝑒 ikx + 𝐺𝑒 −ikx
Where F represent the amplitude of transmitted wave
and B represent the amplitude of reflected wave. But there is no reflection in region 3 and therefore
𝛹3 = 𝐹𝑒 ikx
Since the probability of finding the particle is proportional to the square of the amplitude, tunneling
probabilityis
|𝐹|2
𝑇 = |𝐴|2

Applications
1. Explanation of Zener break down
2. Explanation of Josephson effect / SQUID
Heisenberg’s Uncertainty Principle
The Heisenberg’s uncertainty principle states that it is not possible to find the position and the
momentum of a particle simultaneously with precision. In other words, the product of uncertainty
in the measurement of position (∆x) and uncertainty in the measurement of momentum (∆p) is
greater than or equal to h/2π,
∆p ∆x ≥ℏ

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Similar to above expression, we can write
∆E ∆t ≥ ℏ
where ∆E and ∆t are the uncertainties in determining energy and time, respectively and
∆J ∆θ≥ ℏ
∆J and ∆θ are the uncertainties in the measurement of angular momentum and angle, respectively.
Applications of uncertainty principle
1. Prove that Electron cannot exist inside nucleus

Radii of nucleus are of the order of 10-14m.

∴ Δx= 10-14m

ℏ 1.054𝑥10−34
𝛥𝑝 = = = 1.1𝑥10−20 𝑘𝑔𝑚𝑠 −1
𝛥𝑥 10−14

Momentum of electron is 𝑝 ≈ 1.1𝑥10−20 𝑘𝑔𝑚𝑠 −1

Neglecting rest mass energy, kinetic energy of the electron is 𝐾𝐸 = 𝑝𝑐 =

1.1x10−20 𝑘𝑔𝑚𝑠 −1 x3x108 𝑚𝑠 −1 = 3.3x10−12 𝐽 ≈ 20𝑀𝑒𝑉

So an electron requires 20MeV energy to stay inside nucleus. But experiments shows that electrons
associated with even the unstable atoms never have more than fraction of this energy. Hence we can
conclude that electron cannot be present inside nucleus.

2. Uncertainty in frequency of light emitted by an atom/Natural Line Broadening

Typical lifetime in an excited stat of an atom is 10-8s. So the uncertainty of de-excitation is Δt=10-8s.
The corresponding uncertainty in energy is
ℏ
𝛥𝐸 = and 𝛥𝐸 = ℎ𝛥𝜈
𝛥𝑡
ℏ
ℎ𝛥𝜈 =
𝛥𝑡
ℏ 1 1
𝛥𝜈 = = = ≈ 16𝑀𝐻𝑧
ℎ𝛥𝑡 2𝜋𝛥𝑡 6.28𝑥10−8 𝑠 −1

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