ENGINEERING PHYSICS NP NOTES / 18PHY12/22

MODULE 4
CHAPTER 1 – QUANTUM MECHANICS

The branch of Physics developed after 19th century. It deals with particles of
atomic and subatomic dimensions. All the concepts in Physics developed in and
after 20th century are put under Modern Physics. Before Quantum Mechanics,
classical mechanics ruled the world of Physics. For particles down to atomic and
subatomic dimension, classical mechanics was a failure and hence Quantum
mechanics came into existence. In the beginning, light is considered to have wave
nature and processes like black body radiation, photoelectric effect and like black
body radiation, photo electric effect and Compton effect could not be explained
based on the wave nature.
Wave: A wave is spread out over a relatively large region of space and it cannot
be said to be located just here and there. A wave is specified by its frequency,
wavelength, phase or wave velocity, amplitude and intensity.
Matter: A particle (matter) has mass and it is located at some definite point. The
particle is specified by its mass, velocity, momentum and energy.
Matter waves: The Waves associated with the moving particles of matter are
known as matter waves or pilot waves or de Broglie waves.

Dual nature of matter: Having established the dual nature of energy it did not
take much longer to realise that matter can also exhibit dual nature.

de Broglie hypothesis: In 1924, Louis de Broglie made a daring suggestion that

like radiation (energy) matter also exhibit schedule characteristics. He proposed
the concept of matter waves which was led by the following chain of reasoning.
 The entire universe answers of matter and radiation (energy) only.
 It is well known that nature love symmetry and the two form in which
nature manifests herself are matter and energy.
 If one form namely energy could exhibit a dual nature The Other form
namely matter should also exhibit a dual nature.
 Einstein had a 1905 established the relationship between mass and energy
and said that they are inter-convertible.

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The waves associated with matter are called matter waves or De Broglie waves,
whose wavelength is given by
ℎ
𝜆=
𝑝
Where, λ is the wavelength,
h is Planck’s constant,
p is linear momentum.”

Characteristics of matter waves:

i) Lighter the particle greater is the wavelength associated with it and vice
versa.
ii) Lesser the velocity of the particle, greater is a wavelength associated
with it and vice versa.
iii) For v=0, λ=∞, this means the matter waves are generated by the motion
of particle. If the particle are at rest then there is no meaning of matter
waves associated with them.
iv) Whether the particle is charged or not matter waves is associated with
it. This reveals that matter waves are not electromagnetic but a new kind
of waves.
v) They are called pilot waves in the sense that their only function is to
pilot or guide the material particles.
vi) It can be proved that matter waves can travel faster than light.
vii) No single phenomena exhibit both particle nature and wave nature
simultaneously
viii) They are complex in nature and has no physical significance. The
amplitude of matter waves depend on the probability of finding the
particle.

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de BROGLIE WAVELENGTH OF AN ACCELERATED ELECTRON.

We know that for an electron accelerated under a potential difference of ‘V’, the
energy required will be ‘eV’. If ‘m’ is the mass and ‘v’ is the velocity of an
electron and ‘p’ is the momentum, then the energy for non-relativistic case can
be written as,
1
𝐸 = 𝑚𝑣 2 ----------- (1)
2

𝐸 = 𝑒𝑉 ----------- (2)
By multiply and Divide equation (1) by ‘m’, since momentum 𝑃 = 𝑚𝑣 we get,
𝑝2
𝐸= ----------- (3) Equating equation (1) and (2) we get
2𝑚
𝑝2
𝑒𝑉 = ----------- (4)
2𝑚

∴ 𝑝 = √2𝑚𝑒𝑉 ----------- (5)

According to de Broglie equation for wavelength is given by,
ℎ
𝜆= ----------- (6) Substituting equation (5) in (6) we get
𝑝

𝒉
𝝀= ----------- (7)
√𝟐𝒎𝒆𝑽

Equation (7) is the expression for de Broglie wavelength of an accelerated

particle in general.
𝒉
𝝀𝒆 = ----------- (8)
√𝟐𝒎𝒆𝑽

Equation (8) is the expression for de Broglie wavelength of and accelerated

particle in general. Substituting for the known constants we can calculate 𝝀𝒆
Calculating de Broglie wavelength of an accelerated electron, 𝝀𝒆
h
λe =
√2meV
1 h
λe = ( ) ( )
√V √2me

1 6.625x10−34
λe = ( ) ( )
√V √2(9.11x10−31 )(1.6x10−19 )

𝟏𝟐.𝟐𝟔𝒙𝟏𝟎−𝟏𝟎
𝛌𝐞 = m
√𝐕
𝟏𝟐.𝟐𝟔
𝛌𝐞 = ( ) 𝑨𝟎
√𝐕

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Different forms of de Broglie wavelength

𝒉 𝒉 𝐡 𝐡 𝐡
𝝀 = = = = =
𝒑 𝒎𝒗 √𝟐𝐦𝐄 √𝟐𝐦𝐞𝐕 √𝟑𝐦𝐤𝐓
Where,
λ - de Broglie wavelength of the given particle (m), h - Planck’s constant (Js)
m - Mass of the particle (kg), v - Velocity of the particle (m/s)
E - Kinetic energy of the particle (J), e - Charge of an electron (C)
V - Potential (V), K - Boltzmann’s constant (J/K), T - Temperature (K)
Heisenberg’s Uncertainty Principle (HUP):
It is impossible to specify precisely and simultaneously the values of both
members of particular pair of physical variables that describe the behaviour
of an atomic system, the product of uncertainty or error in the knowledge of
two variables is equal to or greater than h/4π
If ∆ x and Px are the uncertainties in the measurement of position and
momentum of the particle then the uncertainty can be written as
𝒉 𝒉 𝒉
∆𝒙. ∆𝒑𝒙 ≥ 𝟒𝝅 ∆𝑬. ∆𝒕 ≥ 𝟒𝝅 ∆𝑳. ∆ ≥ 𝟒𝝅
∆𝑥 → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛, ∆𝒑𝒙 → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚
∆𝐸 → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑒𝑛𝑒𝑟𝑔𝑦, ∆𝑡 → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑡𝑖𝑚𝑒
∆𝐿 → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚,
∆ → 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑖𝑡𝑦 𝑖𝑛 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛
ℎ → 𝑃𝑙𝑎𝑛𝑐𝑘 ′ 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Physical Significance:
i) It signifies dual nature of matter.
ℎ
ii) From ∆𝑥∆𝑝 ≥ , it is clear that if ∆𝑥 decreases then ∆𝑝 increases. If
4𝜋
we try to measure x accurately, the error in measuring p increases,
which will lead to the measurement of absurd values. Hence it is always
proper to measure the most probable value of physical quantity than
accurate values.

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APPLICATION OF HEISENBERG’S UNCERTAINTY PRINCIPLE

1. Non-existence of electron inside the nucleus

Using the HUP, we can prove that electrons cannot reside inside the nucleus.
Let us assume that the electrons are inside the nucleus. The maximum uncertainty
in measuring the position of electron is equal to the diameter of the nucleus i.e.
10-14m.
ℎ
∴ ∆𝑥 = 10−14 𝑚 Using, ∆𝑥∆𝑝 ≥
4𝜋
ℎ
∆𝑝 ≥
4𝜋 𝑥 10−14

6.625 𝑥 10−34
≥ ≥ 0.5 𝑥 10−20 𝑘𝑔𝑚/𝑠
4 𝑥 𝜋 𝑥 10−14
Let us consider ∆𝑝 ≃ 𝑝 and putting this in total energy equation,
𝑃2
𝐸= We get
2𝑚
(5.21𝑥10−21 )2 1.4897x10−11
𝐸= = 1.4897x10-11J = eV
2𝑥9.11𝑥10−31 1.6𝑥10−19

∴ 𝐸 = 92.9 𝑀𝑒𝑉
If an electron is inside the nucleus its energy (least) should be 92.9 MeV. But
experimentally investigation on β- decay reveal that, kinetic energy of β-particles
(which are similar to electrons), is of the order of 3 to 4 MeV. Therefore, the
assumption we have made is wrong. This explains why an electron cannot exist
inside the nucleus. ∴ Electrons cannot reside inside the nucleus.
Wave function (𝝍): A function of position and time, which gives information
about a particle completely. Usually wave functions are complex in nature.
Wave function is related the probability of finding the particle at a given place
and given time.
The quantity that characterized the de Broglie wave is called the wave function
it is usually denoted by 𝝍(𝒓 ⃗ , 𝒕) it is a function of space variable ‘𝒓
⃗ (𝒙, 𝒚, 𝒛)’ and
time‘t’. This gives complete information about the state of system at a particular
time. It is also called the state function and represents the probability amplitude
if 𝝍 is large the probability of finding a particle is also a large, if 𝝍 small the
probability of finding the particle is small.

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Significance of 𝝍 (physical interpretation of ; Max-Born interpretation;

Normalisation condition):

𝜓 has no physical significance. It is | 𝜓 2 | which has the significance. | 𝜓 2 | is

called probability density function.It is the probability of finding a particle in unit
volume. The probability of finding a particle per unit volume = | 𝜓| 2 .
Let us consider a particle in a volume V, which is divided into elementary
volumes dV.
∴ Probability of finding the particle in volume dV = | 𝜓| 2 𝑑𝑉

The probability of finding the particle in volume V = ∫𝑉 | 𝜓| 2 𝑑𝑉

Since, the particle is present in the volume, probability of finding it is 1.
+∞

∴ ∫ | 𝜓| 2 𝑑𝑉 = 1
−∞

This is called normalization condition, Max-Born interpretation or significance

of 𝜓.
PROPERTIES OF WAVE FUNCTION
Wave function 𝜓 is an acceptable function if agrees as follows,
i) 𝜓 should be single valued w.r.t x
ii) 𝜓 should be continuous w.r.t to x
iii) 𝜓 should be Finite
iv) For bound states ‘ψ’ must vanish at potential boundary and outside. If
‘ψ*’ is a complex function, then ψ* ψ must also vanish at potential
boundary and outside.

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Multiple valued Discontinuous Infinite

1. Single valued
2. Finite
3. Continuous

Schrodinger wave equation describes the wave function or state function. There
are two types of Schrodinger equations, time-dependent Schrodinger wave
equation, and time-independent Schrodinger wave equation. These equations
were presented by Ervin Schrodinger in 1925.
In classical mechanics, the motion of a body is given by Newton’s second law of
motion. But elementary particles like electron, protons, and photons possess wave
properties as well, therefore another equation instead of Newton’s second law
equation (F=ma) is required for describing their motion.
The new equation must take into account wave properties of particles and it
should, therefore, be similar to the equation describing wave on strings acoustic
waves or electromagnetic waves. This equation was found in 1926 by the
Austrian physicist Schrodinger and is known after his name as Schrodinger wave
equation.

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SCHRODINGER’S TIME INDEPENDENT WAVE EQUATION IN 1D

Consider a wave function describing de Broglie wave moving in positive x
direction represented by following in complex notation,
𝜓(𝑥) = 𝐴𝑒 −𝑖(𝜔𝑡−𝑘𝑥) ---------- (1)
Where, 𝜓is the wave function, A is the constant, ω is the angular frequency,
2𝜋
𝜔 = 2𝜋ν , k is the propagation constant or wave vector, 𝑘 = , x is the
𝜆
ℎ
displacement, t is the instant of time, ℏ = is the angular Planck’s constant
2𝜋

We know that,
𝐸
𝜔 = 2𝜋𝜈 = ----------- (2)
ℏ
2𝜋 𝑝
𝑘= = ---------- (3)
𝜆 ℏ

Substitute for ω and k in terms of E and p in equation (1) we get,

𝐸 𝑝
−𝑖( 𝑡− 𝑥)
𝜓(𝑥) = 𝐴𝑒 ℏ ℏ
𝑖
𝜓(𝑥) = 𝐴𝑒 −ℏ(𝐸𝑡−𝑝𝑥) ---------- (4)
Differentiate equation (4) wrt x we get,
𝑑𝜓(𝑥) 𝑖𝑝 − 𝑖 (𝐸𝑡−𝑝𝑥) 𝑖𝑝
= 𝐴𝑒 ℏ = 𝜓(𝑥)
𝑑𝑥 ℏ ℏ
𝑑 2 𝜓(𝑥) 𝑖 2 𝑝2 − 𝑖 (𝐸𝑡−𝑝𝑥) 𝑖 2 𝑝2
= 2 𝐴𝑒 ℏ = 2 𝜓(𝑥)
𝑑𝑥 2 ℏ ℏ
𝒅𝟐 𝝍(𝒙) 𝒑𝟐
=− 𝝍(𝒙) ------------ (5)
𝒅𝒙𝟐 ℏ𝟐

Total energy of the system is sum of kinetic energy and potential energy, then
total energy of particle with mass ‘m’ moving with velocity ‘v’ is given by
1
E = KE + PE, 𝐸 = 𝑚𝑣 2 + 𝑉
2

𝑝2
𝐸= +𝑉
2𝑚
𝑝2 = 2𝑚(𝐸 − 𝑉) ---------- (6)

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Substitute equation (6) in equation (5), we get

𝑑2 𝜓(𝑥) 2𝑚(𝐸 − 𝑉)
=− 𝜓(𝑥)
𝑑𝑥 2 ℏ2
𝑑2 𝜓(𝑥) 2𝑚(𝐸−𝑉)
+ 𝜓(𝑥) = 0 ---------- (7)
𝑑𝑥 2 ℏ2
𝒅𝟐 𝝍(𝒙) 𝟖𝝅𝟐 𝒎
𝒅𝒙𝟐
+ 𝒉𝟐
(𝑬 − 𝑽)𝝍(𝒙) = 𝟎 ---------- (8)
Above is the Schrodinger’s time independent wave equation in 1dimension

𝒅𝟐 𝝍(𝒙) 𝒅𝟐 𝝍(𝒚) 𝒅𝟐 𝝍(𝒛) 𝟖𝝅𝟐 𝒎

+ + + (𝑬 − 𝑽)𝝍(𝒙, 𝒚, 𝒛) = 𝟎
𝒅𝒙𝟐 𝒅𝒚𝟐 𝒅𝒛𝟐 𝒉𝟐
𝒅𝟐 𝝍(𝒙) 𝒅𝟐 𝝍(𝒚) 𝒅𝟐 𝝍(𝒛)
Laplacian Operator + + = 𝛁𝟐 ψ(x,y,z)
𝒅𝒙𝟐 𝒅𝒚𝟐 𝒅𝒛𝟐

𝟐
𝟖𝝅𝟐 𝒎
𝛁 𝝍(𝒙, 𝒚, 𝒛) + (𝑬 − 𝑽)𝝍(𝒙, 𝒚, 𝒛) = 𝟎
𝒉𝟐

EIGEN ENERGY VALUES AND EIGEN WAVE FUNCTION

The wave function 𝜓(𝑥) satisfied all condition for the SWE equation. The
allowed energy in quantum mechanics is not continuous but discrete. Since SWE
is second order differential equation there is not one but several solutions. Such
wave functions which are acceptable to the physical system are called Eigen wave
functions. Acceptable discrete energies are called Eigen energy values and the
corresponding states are called Eigen energy States.
Requirement of finiteness and continuity of the wave function brings about the
discrete energy eigenvalue and occur because the particle motion accompanies
the wave function, i,e., due to the particle wave duality.

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APPLICATION OF SCHRODINGER’S WAVE EQUATION FOR A

PARTICLE IN 1D BOX:
Particle in a one dimension potential well of infinite height (or) particle in a
box of finite width and infinite potential.
Consider a potential well of width ‘a’ and height∞.
Particle is inside the well where V=0. Outside and on
the walls of the well V =∞. We are going to find the
Eigen function and Eigen values for the particle.
We know that,
𝑑 2 𝜓(𝑥) 8𝜋 2 𝑚
+ (𝐸 − 𝑉)𝜓(𝑥) = 0 … … … (1)
𝑑𝑥 2 ℎ2
Outside the well V=∞
𝑑 2 𝜓(𝑥) 8𝜋 2 𝑚
∴ + (𝐸 − ∞)𝜓(𝑥) = 0 … … … … … (2)
𝑑𝑥 2 ℎ2
The above equation is true only for 𝜓(𝑥) = 0
∴ 𝜓(𝑥) = 0 𝑎𝑡 𝑥 = 0 & 𝑥 = 𝑎
Inside the well V = 0
𝑑 2 𝜓(𝑥) 8𝜋 2 𝑚
∴ + (𝐸 − 0)𝜓(𝑥) = 0
𝑑𝑥 2 ℎ2
𝑑 2 𝜓(𝑥) 8𝜋 2 𝑚𝐸
∴ + 𝜓(𝑥) = 0 − − − − − (3)
𝑑𝑥 2 ℎ2
8𝜋 2 𝑚𝐸
𝐿𝑒𝑡 = 𝑘 2 … … … … … (4)
ℎ2

8𝜋 2 𝑚𝐸
𝑘=√
ℎ2

𝑑 2 𝜓(𝑥)
2
+ 𝑘 2 𝜓(𝑥) = 0 … … … … … … . (5)
𝑑𝑥
The solution of equation (4) is
𝜓(𝑥) = 𝐴 𝑐𝑜𝑠𝑘𝑥 + 𝐵 sin 𝑘𝑥 … … … … … . (6)
𝐴𝑡 𝑥 = 0, 𝜓(0) = 0

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∴ 𝐴 = 0 … … … … … . . (7)

Hence 𝝍(𝒙) = 𝑩 𝒔𝒊𝒏𝒌𝒙 … … … … … … . (𝟖)

𝐴𝑡 𝑥 = 𝑎, 𝜓(𝑎) = 0
∴ 𝐵 sin 𝑘𝑎 = 0
B≠ 0, (If B = 0 the 𝜓(𝑥)= everywhere)
∴ sin 𝑘𝑎 = 0
𝑘𝑎 = sin−1 0
𝑘𝑎 = 𝑛𝜋
𝒏𝝅
𝒌= − − − −(9)
𝒂

𝟐
𝒏𝟐 𝝅𝟐
𝒌 = − − − − − (10)
𝒂𝟐
Substitute for 𝑘 2 from equation (4) in equation (10) we get,
8𝜋 2 𝑚𝐸 𝑛2 𝜋 2
=
ℎ2 𝑎2
𝒏 𝟐 𝒉𝟐
𝑬= − − − − − − − − − (𝟏𝟏)
𝟖𝒎𝒂𝟐
Where, n = 1,2,3,…….[n = 0 not allowed as 𝜓 = 0 at n =0]
The value of energy for n = 1 is called zero point energy or ground state energy.
𝒉𝟐
∴ 𝑬𝟏 =
𝟖𝒎𝒂𝟐
The values of energy for n = 2, 3, 4 ……….. are called excited states.
𝟒𝒉𝟐
𝑬𝟐 = = 𝟒𝑬𝟏
𝟖𝒎𝒂𝟐
𝟗𝒉𝟐
𝑬𝟑 = = 𝟗𝑬𝟏
𝟖𝒎𝒂𝟐
𝒏𝒉𝟐
𝑬𝒏 =
𝟖𝒎𝒂𝟐
∴ The Energy of the particle is quantized.
𝑬𝟏 , 𝑬𝟐 , 𝑬𝟑 , … … … … … … 𝒂𝒓𝒆 𝒄𝒂𝒍𝒍𝒆𝒅 𝒂𝒔 𝑬𝒊𝒈𝒆𝒏 𝒆𝒏𝒆𝒓𝒈𝒚 𝒗𝒂𝒍𝒖𝒆𝒔
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To Evaluate B:
We have following from equation (8)
𝜓(𝑥) = 𝐵 𝑠𝑖𝑛𝑘𝑥
Using normalization condition for 1 dimension
𝑎

∫ |𝜓(𝑥)|2 𝑑𝑥 = 1 − − − − − − − − − −(12)
0
𝑎
∫𝑜 𝐵2 𝑠𝑖𝑛2 𝑘𝑥 𝑑𝑥 = 1 Multiply and divide by 2,
𝑎
𝐵2 2𝑠𝑖𝑛2 𝑘𝑥
∫ 𝑑𝑥 = 1 𝑈𝑠𝑖𝑛𝑔 {2𝑠𝑖𝑛2 𝜃 = 1 − 𝑐𝑜𝑠2𝜃} 𝑤𝑒 𝑔𝑒𝑡
2
0
𝑎
𝐵2
∫ (1 − 𝑐𝑜𝑠2𝑘𝑥)𝑑𝑥 = 1
2
0
𝑎 𝑎
𝐵2 2𝑛𝜋𝑥 𝑛𝜋
[∫ 1. 𝑑𝑥 − ∫ 𝑐𝑜𝑠 𝑑𝑥] = 1 𝑆𝑖𝑛𝑐𝑒 𝑘 =
2 𝑎 𝑎
0 0
𝑎
𝐵2
[∫ 1. 𝑑𝑥 − 0] = 1
2
0

𝐵2 𝑎 2
∴ = 1; 𝐵2 = ;
2 𝑎

𝟐
𝑩 = ±√ − − − − − − − (13)
𝒂

Substituting for B in equation(8) we get wave function as,

2
𝜓(𝑥) = ±√ 𝑠𝑖𝑛𝑘𝑥
𝑎

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𝟐 𝒏𝝅
𝝍𝒏 (𝒙) = ±√ 𝒔𝒊𝒏 ( ) 𝒙
𝒂 𝒂

2 𝜋
𝜓1 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
𝑎 𝑎

2 2𝜋
𝜓2 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
𝑎 𝑎

2 3𝜋
𝜓3 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
𝑎 𝑎

𝝍𝟏 (𝒙), 𝝍𝟐 (𝒙), 𝝍𝟑 (𝒙) … … … … … … . . 𝒂𝒓𝒆 𝒄𝒂𝒍𝒍𝒆𝒅 𝒂𝒔 𝑬𝒊𝒈𝒆𝒏 𝒘𝒂𝒗𝒆𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏𝒔

𝟐 𝒏𝝅
|𝝍𝒏 (𝒙)|𝟐 = 𝒔𝒊𝒏𝟐 ( ) 𝒙 … … … … … … . 𝑷𝒓𝒐𝒃𝒂𝒃𝒊𝒍𝒊𝒕𝒚 𝒅𝒆𝒏𝒔𝒊𝒕𝒚
𝒂 𝒂

Case i): n = 1,
ℎ2 2 𝜋
𝐸1 = 𝜓1 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
8𝑚𝑎2 𝑎 𝑎

At x = 0 & x = a, 𝜓1 (𝑥) = 0. ∴ |𝜓1 (𝑥)|2 = 0

Hence the probability of locating the particle at walls = 0
𝑎 2 2
when x = 𝜓= √ ∴ |𝜓|2 = ( 𝑚𝑎𝑥𝑖𝑚𝑢𝑚)
2 𝑎 𝑎

Hence the particle is located mostly at the centre of the well.

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1 1
2

x=0 a/2 x=a x=0 a/2 x=a

Case ii): n = 2

4ℎ2 2 2𝜋
𝐸2 = 𝜓2 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
8𝑚𝑎2 𝑎 𝑎

At x = 0, x = a, x = a/2, 𝜓2 (𝑥) = 0. ∴ |𝜓2 (𝑥)|2 = 0

∴ The probability of locating the particle at the walls and at the center of the well
=0
𝑎 3𝑎 2 2
At 𝑥= , ; 𝜓= √ (or) |𝜓|2 = (maximum)
4 4 𝑎 𝑎

∴ The probability of locating the particle at 1/4 & 3/4 of well width is maximum.

ψ2 | ψ2|2
a/4 3a/4
a/4
3a/4
x=0 a/2 x=a x=0 a/2 x=a

Case iii) : n = 3

9ℎ2 2 3𝜋
𝐸3 = 𝜓3 (𝑥) = ±√ 𝑠𝑖𝑛 ( ) 𝑥
8𝑚𝑎2 𝑎 𝑎
𝑎 2𝑎
At x = 0, x = a, 𝑥 = , ; 𝜓 = 0. ∴ |𝜓|2 = 0
3 3

𝑎 3𝑎 5𝑎 2 2
At 𝑥 = , , ; 𝜓= √ (or) |𝜓|2 = (maximum)
6 6 6 𝑎 𝑎

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B) Free particle: A free particle is one which moves without any boundaries and
V=0
𝑑 2 𝜓(𝑥) 8𝜋 2 𝑚
+ (𝐸 − 0)𝜓(𝑥) = 0
𝑑𝑥 2 ℎ2
8𝜋 2 𝑚
𝐿𝑒𝑡 𝐸 = 𝑘 2 … … … … … (4)
ℎ2

𝑑 2 𝜓(𝑥)
+ 𝑘 2 𝜓(𝑥) = 0
𝑑𝑥 2
Whose, general solution is
𝜓 = 𝐴 𝑐𝑜𝑠𝑘𝑥 + 𝐵 sin 𝑘𝑥 , Where A, B, k are constants.
Since there are no boundary conditions, A, B & k can have any values. The
energy E is,
𝑘 2 ℎ2
𝐸=
8𝜋 2 𝑚

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The value of E is not quantized for a free particle. Thus free particle is a classical
entity.

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