PRINCIPLES OF QUANTUM MECHANICS

Introduction: Quantum mechanics is a new branch of study in physics which is indispensable in

understanding the mechanics of particles in the atomic and sub-atomic scale.
The motion of macro particles can be observed either directly or through microscope.
Classical mechanics can be applied to explain their motion. But classical mechanics failed to
explain the motion of micro particles like electrons, protons etc...
Max Plank proposed the Quantum theory to explain Blackbody radiation. Einstein applied
it to explain the Photo Electric Effect. In the mean time, Einstein’s mass – energy relationship (E
= mc2) had been verified in which the radiation and mass were mutually convertible. Louis de
Broglie extended the idea of dual nature of radiation to matter, when he proposed that matter
possesses wave as well as particle characteristics.

Waves and Particles: de Broglie suggested that the radiation has dual nature, i.e. both particle as
well as wave nature. The concept of particle is easy to grasp. It has mass, velocity, momentum
and energy. The concept of wave is a bit more difficult than that of a particle. A wave is spread
out over a relatively large region of space, it cannot be said to be located just here and there, and
it is hard to think of mass being associated with a wave. A wave is specified by its frequency,
wavelength, phase, amplitude, intensity.
Considering the above facts, it appears difficult to accept the conflicting ideas that radiation
has dual nature. However this acceptance is essential because radiation sometimes behaves as a
wave and at other times as a particle.
(1) Radiations behaves as waves in experiments based on interference, diffraction, polarization
etc. this is due to the fact that these phenomena require the presence of two waves at the
same position and at the same time. Thus we conclude that radiation behaves like wave.
(2) Plank’s quantum theory was successful in explaining blackbody radiation, photoelectric
effect, Compton effect and had established that the radiant energy, in its interaction with
the matter, behaves as though it consists of corpuscles. Here radiation interacts with matter
in the form of photons or quanta. Thus radiation behaves like particle.
Hence radiation cannot exhibit both particle and wave nature simultaneously.

de BROGLIE HYPOTHESIS:

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 In 1924, de Broglie extended the dual nature to material particles or micro particles like
electrons, protons, neutrons etc. according his hypothesis, when particles are accelerated then they
will spread like a wave with a certain wavelength The dual nature of light possessing both wave
and particle properties was explained by
According to Planck the energy of a photon of frequency ν can be expressed as
E = hν ------ (1)
Where h is the Planck’s constant (h=6.625 × 10-34J-s)
According to Einstein, the energy of the photon of mass m can be expressed as
E = mc2 ----- (2)
Where c is the velocity of light (c = 3 × 108 m/s)
From eq. (1) and (2), we get,
hν = mc2
ℎ𝑐 𝑐
= 𝑚𝑐 2 (𝑠𝑖𝑛𝑐𝑒, 𝜈 = 𝜆)
𝜆
ℎ
𝜆=
𝑚𝑐

Where, mc = p, the momentum of photon.

ℎ
𝜆=𝑝

λ is de Broglie wavelength associated with a photon.

de Broglie proposed the concept of matter waves , according to which a material particle
of mass ‘m’ moving with velocity ‘v’ should be associated with de Broglie wavelength ‘λ’ given
by,
ℎ ℎ
𝜆= =𝑝 ----------- (3)
𝑚v

The above eqn. (3) represents de Broglie wave eqn.

de Broglie wavelength of electrons: According to de Broglie hypothesis, if an electron of charge,
‘e’, mass ‘m’ is moving with a velocity ‘v’ in the presence of potential ‘V’ then,
The energy of electron in terms of potential can be expressed as,
E = eV -------- (4)
The kinetic energy gained by the electron in the potential V can be expressed as
1
𝐸= 𝑚v 2 ------ (5)
2

From eqn. (4) and (5), we get,

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 1 1 p2
𝑒𝑉 = 𝑚v 2 ⟹ 𝑚𝑒𝑉 = 𝑚2 v 2 = (Since, mv = p)
2 2 2

𝑝 = √2𝑚𝑒𝑉 ------- (6)

Substituting eqn. (6) in eqn. (3), the wavelength associated with the electron will be
𝒉 𝒉
𝝀= = ------ (7)
√𝟐𝒎𝒆𝑽 √𝟐𝒎𝑬

Substituting, Planck’s constant (h=6.625 × 10-34J-s), mass of electron (m=9.1 × 10-31Kg) and
charge of electron (e=1.6 × 10-19C), we get,
6.625 × 10−34J−s
𝜆=
√2×9.1 × 10−31 Kg×1.6 × 10−19C ×𝑉

12.27
𝜆= × 10−10𝑚
√𝑉
𝟏𝟐.𝟐𝟕
𝝀= Å -------- (8)
√𝑽
Eqn. (8) shows the wavelength associated with an electron in the presence of potential V in volts.

MATTER WAVES:
de Broglie proposed the dual nature of the radiation. According to his hypothesis, “a
moving particle has associated with a wave irrespective of its nature” (charged or neutral) is called
matter waves.
Properties (characteristics) of matter waves:
ℎ
Since 𝜆 =
𝑚v
1) Lighter the particle, greater is the wavelength associated with it.
2) Lesser the velocity of the particle, longer the wavelength associated with it.
3) For v = 0, λ = ∞. This means that only with moving particle, matter waves is associated.
4) It can be proved that matter waves travel faster than light velocity.
We know that E = hν and E = mc2
𝑚𝑐 2
⟹ ℎ𝜈 = 𝑚𝑐 2 𝑜𝑟 𝜈 = ℎ
Wave velocity (ωp) is given by
𝑚𝑐2 ℎ ℎ
𝜔𝑝 = 𝜈𝜆 = ℎ
× 𝑚v (𝑆𝑖𝑛𝑐𝑒, 𝜆 = 𝑚v)
𝒄𝟐
⇒ 𝝎𝒑 =
𝒗

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As the particle velocity ‘v’ cannot exceed the velocity of light ‘c’, ω p is always greater than the
velocity of light.
5) Matter waves are not electromagnetic waves. They are some special kind of waves called ‘pilot
waves’, because which guide the particle.
6) No single phenomena exhibit both particle nature and wave nature simultaneously.
7) The wave nature of matter introduces an uncertainty in the location of the particle & the
momentum of the particle exists when both are determined simultaneously.

DAVISSON AND GERMER’S EXPERIMENT:

First practical evidence for the matter waves was given by C.H. Davisson and L.H. Germer
in 1927. This was the first experimental support to de Broglie’s hypothesis.
Experimental arrangement: The experimental
arrangement is shown in fig. 1. It consists of three
parts. They are electron gun, target set up and
circular scale arrangement.
An electron gun, which comprises of a
tungsten filament (F) is heated by a low tension
battery B1, produces electrons. These electrons are
accelerated to desired velocity by applying suitable
potential from a high tension source B2. The
accelerated electrons are collimated into a fine beam by allowing them to pass through a system
of pin holes provided in the cylinder (C). The whole instrument is kept in an evacuated chamber.
The past moving beam of electrons is made to strike the Nickel target capable of rotating
about an axis perpendicular to the plane. The electrons are now scattered in all directions by the
atomic planes of crystals. The intensity of the electron beam scattered in a direction can be
measured by the electron collector which can be rotated about the same axis as the target. The
collector is connected to a galvanometer whose deflection is proportional to the intensity of the
electron beam entering the collector.
Calculation of wavelength associated with electrons:
When a potential of 54V is applied, the first order maximum is observed at an angle of 50o between
incident and reflected rays. The plot of variation of number of scattering electrons with angle of

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diffraction is shown in fig. The plot of variation of number of scattering electrons with angle of
diffraction is shown in fig. Hence, the angle of diffraction is 65 o(since, 2θ+50o=180) shown in
below fig. the inter-planar spacing, d of Nickel crystal is 0.91Ao, which is measured by the x-ray
diffraction method.

From Bragg’s Law, 2d sinθ = nλ

Substituting the value of d, θ and n, we get,
2 × 0.91 × sin(65𝑜 ) = 1𝜆 (for First order diffraction, n=1)
𝜆 = 1.65 × 10−10𝑚
𝝀 = 𝟏. 𝟔𝟓 Å -------------- (1)
The de Broglie’s wavelength associated with the electron, when a potential difference of 54 Vis
applied,
12.27 12.27
𝜆= = = 𝟏. 𝟔𝟔𝟕Å ---------- (2)
√𝑉 √54
From (1) and (2), it can be concluded that, the wavelengths of the electron beam calculated from
Bragg’s law and de Broglie’s equation are in very good agreement. Hence, the wave nature of the
particle is proved experimentally.

HEISENBERG’S UNCERTAINTY PRINCIPLE:

Statement: It is impossible to measure any two pair of quantities like position and momentum
etc., simultaneously.
Since a moving particle has to be regarded as a de Broglie group, there is a limit to the
accuracy with which we can measure the particle properties. The particle may be found anywhere
within the wave group, moving with the group velocity. If the group is narrow, it is easy to locate
its position but the uncertainty in calculating its velocity or momentum increases. On the other
hand, if the group is wide, its momentum can be estimated satisfactorily, but the uncertainty in
finding the location of the particle is great. Heisenberg stated that the simultaneous determination
of exact position and momentum of a moving particle is impossible.

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 If ∆x, the error in measuring the position is small then ∆p, the error in measuring
momentum will be large and vice-versa. It means that if one quantity is measured accurately, the
other quantity becomes less accurate.
ℏ ℎ
i.e., ∆𝑥 × ∆𝑝 ≥ 2 𝑜𝑟 ---------- (1)
4𝜋

Thus any instrument cannot measure both quantities more accurately than predicted by
Heisenberg’s principle of uncertainty.
The same relation holds for the energy and time, if ∆E is the error in measuring energy and
∆t is the error in measuring time then,
ℏ ℎ
∆𝐸 × ∆𝑡 ≥ 2 𝑜𝑟 ------------ (2)
4𝜋

• According to classical theory, it is possible to occupy a fixed position and have a definite
momentum, therefore, it is possible to predict neatly its position and momentum.
• But, according to uncertainty principle, it is not possible to determine accurately the
simultaneous values of position and momentum of s particle at any given time.
ILLUSTRATION – WHY AN ELECTRON CANNOT EXIST IN THE NUCLEUS?
Let us assume that electrons exist in the nucleus. As the radius of the nucleus in
approximately 10-15 m. If electron is to exist inside the nucleus, then uncertainty in the position of
the electron is given by
∆x= 10-15 m
According to Heisenberg’s uncertainty principle,
ℎ
∆x.∆p = 2𝜋
ℎ 6.626 ×10−34
Thus, ∆p = 2𝜋×∆𝑥 = = 0.5266 × 10−19𝑘𝑔𝑚/𝑠
2×3.14×10−15

If this is p the uncertainty in the momentum of electron, then the momentum of electron
should be at least of this order, that is 0.5266 × 10−19 𝑘𝑔𝑚/𝑠.
An electron having this much high momentum must have a velocity comparable to the
velocity of light. Thus, its energy should be calculated by the following relativistic formula
𝐸 2 = 𝑝2 𝑐 2 + 𝑚𝑜2 𝑐 4
𝐸 2 = [(0.5266 × 10−19)2 × (3 × 108 )] + [(9.1 × 10−31 )2 × (3 × 108 )4 ]
𝐸 2 = 2.4958 × 10−22 𝐽
𝐸 = 1.5798 × 10−11 𝐽

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 1.5798 ×10−11
𝐸= 𝑒𝑉 = 108𝑒𝑉
1.6×10−19

E = 100 MeV

Therefore, if the electron exists in the nucleus, it should have energy of the order of 100MeV.
However, it is observed that beta-particles (electrons) ejected from the nucleus during β–decay
have energies of approximately 3MeV, which is quite different from the calculated value of
100MeV. Second reason that electron cannot exist inside the nucleus is that experimental results
show that no electron or particle in the atom possess energy greater than 4MeV.
Therefore, it is confirmed that electrons do not exist inside the nucleus.

SCHRÖDINGER’S TIME INDEPENDENT WAVE EQUATION:

Schrödinger, in 1926, developed wave equation for the moving particles. One of its forms
can be derived by simply incorporating the de Broglie wavelength expression into the classical
wave eqn. If a particle of mass ‘m’ moving with velocity ‘v’ is associated with a group of waves.
Let ψ be the wave function of the particle. Also let us consider a simple form of progressing
wave like the one represented by the following equation,
Ψ = Ψo sin (ωt – kx) --------- (1)
Where Ψ = Ψ (x, t) and Ψo is the amplitude.
Differentiating Ψ partially w.r.to x,
𝜕Ψ
= Ψo cos (ωt – kx) (- k)
𝜕𝑥

= -k Ψo cos (ωt – kx)

Once again differentiate w.r.to x
𝜕2 Ψ
= (- k) Ψo (- sin (ωt – kx)) (- k)
𝜕 𝑥2

= - k2 Ψo sin (ωt – kx)

𝜕2 Ψ
= - k2ψ (from eqn. (1))
𝜕 𝑥2
𝜕2 Ψ
+ k2ψ = 0 ----------- (2)
𝜕 𝑥2
𝜕2 Ψ 4𝛱 2 2𝛱
+( )ψ = 0 --------- (3) (since k = )
𝜕 𝑥2 𝜆2 𝜆

From eqn. (2) or eqn. (3) is the differential form of the classical wave eqn. now we incorporate
ℎ
De Broglie wavelength expression, λ = 𝑚 𝑣. Thus we obtain,

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 𝜕2 Ψ 4𝛱 2
+( ℎ2
)ψ = 0
𝜕𝑥 2
𝑚2 v2

𝜕2 Ψ 4𝛱 2𝑚 2 v2
+( )ψ = 0 ------- (4)
𝜕𝑥 2 ℎ2

The total energy E of the particle is the sum of its kinetic energy K and potential energy V
i.e., E = K + V -------------- (5)
1
and K = 2 𝑚v 2 -------------- (6)

Therefore, m2v2 = 2m (E – V) --------- (7)

From eqn. (4) and (7), we get,
𝜕2Ψ 4𝛱 2×2𝑚(𝐸−𝑉)
+( )ψ = 0 ------------ (8)
𝜕𝑥 2 ℎ2
ℎ
In quantum mechanics, the value 2𝛱 occurs more frequently. Hence we denote,
ℎ
ℏ = 2𝛱

Using this notation, we have,

𝝏𝟐 𝚿 𝟐𝒎
+ (𝑬 − 𝑽)ψ = 0 -------- (9)
𝝏𝒙𝟐 ℏ𝟐

This is known as one-dimensional Schrodinger’s time independent wave equation which

explains the motion of a charged particle in a potential V.
Extending eqn. (9) for a three – dimensional, we have,
𝜕2 Ψ 𝜕2 Ψ 𝜕2 Ψ 2𝑚
+ + + (𝐸 − 𝑉)ψ = 0 ---- (10)
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℏ2

𝝏𝟐 𝝏𝟐 𝝏𝟐
Using the Laplacian operator, 𝛁 𝟐 = + 𝝏𝒚𝟐 + 𝝏𝒛𝟐
𝝏𝒙𝟐

Eqn. (10) can be written as,

𝟐𝒎
𝛁 𝟐 𝛙+ (𝑬 − 𝑽)ψ = 0 -------- (11)
ℏ𝟐
This is the Schrödinger Time Independent Wave Equation in three dimension.

PHYSICAL SIGNIFICANCE OF WAVE FUNCTION, Ψ:

Max Born in 1926 gave a satisfactory interpretation of the wave function ψ associated with
a moving particle. He postulated that the square of the magnitude of the wave function |ψ|2 (or ψ
ψ* it ψ is complex), evaluated at a particular point represents the probability of finding the particle
at the point. |ψ|2 is called the probability density and ψ is the probability amplitude. Thus the

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probability of the particle within an elemental volume dV is |ψ|2dV. Since the particle is certainly
somewhere, the integral at |ψ|2dV over all space must be unity i.e.
∞

∫ |𝛙|𝟐 𝒅𝑽 = 𝟏.
−∞
A wave function that obeys the above equations is said to be normalized. Energy acceptable
wave function must be normalizable. An acceptable wave function should fulfill the following
requirements (limitations):
1. It must be finite everywhere.
2. It must be single valued.
3. It must be continuous and have a continuous first derivative everywhere.
The normalizing condition for the wave function for the motion of a particle in one dimension is,
∞

∫ |𝛙|𝟐 𝒅𝒙 = 𝟏.
−∞

PARTICLE IN ONE DIMENSIONAL POTENTIAL BOX:

Consider a particle of mass ‘m’ placed inside a one-dimensional box of infinite height and
width L
Assume that the particle is freely moving inside the box. The
motion of the particle is restricted by the walls of the box. The
particle is bouncing back and forth between the walls of the box at
x = 0 and x = L. For a freely moving particle within the potential
box, the potential energy is zero, but abruptly to infinity at x = 0 and
x =L as shown in fig.
0, 0<𝑥<𝐿
i.e., 𝑉(𝑥) = {
∞, 𝑥 ≥ 0 𝑜𝑟 𝑥 ≤ 0
The Schrödinger one – dimensional time independent eqn. is
𝜕2 Ψ 2𝑚
+ (𝐸 − 𝑉)ψ = 0 --------- (1)
𝜕𝑥 2 ℏ2

For freely moving particle V = 0,

𝜕2 Ψ 2𝑚𝐸
+ ψ = 0 ----------- (2)
𝜕𝑥 2 ℏ2
2𝑚𝐸
Taking = 𝑘 2 ---------- (3)
ℏ2

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 𝜕2 Ψ
Equation (2) becomes + k2ψ = 0 ------ (4)
𝜕𝑥 2

Eqation (2) is similar to eqn. of harmonic motion and the solution of above eqn. is written as
Ψ(x) = A sin kx + B cos kx ----------- (5)
where A, B and k are unknown quantities and to calculate them it is necessary to construct
boundary conditions.

Hence boundary conditions are

i. When x = 0, ψ(x) = 0, since V(x) is infinite at x = 0,
ii. When x = L, ψ(x) = 0, since V(x) is infinite at x = L
Substituting the first boundary condition in equation (5), we get,
0 = A sin k(0) + B cos k(0) ⟹ B = 0 ----- (6)
Substituting, the second boundary condition in eqn. (5) we get,
0 = A sin kL + B cos kL -------- (7)
But from eqn. (6) B = 0, therefore eqn (7) may turn as
⟹ A sin kL + 0 × cos kL = 0
⟹ A sin (kL) = 0
⟹ sin (kL) = 0 (since A ≠ 0)
𝑛𝜋
i.e., kL = nπ ⟹ 𝑘 = 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, … -------- (8)
𝐿

Substituting the eqn. (6) and eqn. (8) in eqn. (5), we get,
𝒏𝝅𝒙
𝝍(𝒙) = 𝑨 𝒔𝒊𝒏 ( ) ----------- (9)
𝑳

In order to find the value of A, then we must normalize the wave function. We recognize that the
particle is definitely present inside the box. |ψ|2 is the probability of finding the particle at a
particular point in space, so the integral of this value over all x must be equal to 1:
𝑳
∫𝟎 |𝛙(𝒙)|𝟐 𝒅𝒙 = 𝟏 ------- (10)
Substituting eqn. (9) in eqn. (10), we get,
𝑳 𝒏𝝅𝒙 𝑳𝟏 𝟐𝒏𝝅𝒙
∫𝟎 𝑨𝟐 𝒔𝒊𝒏𝟐 ( 𝑳
) 𝒅𝒙 = 𝟏 ⟹ 𝑨𝟐 ∫𝟎 𝟐
[𝟏 − 𝒄𝒐𝒔 ( 𝑳
)] 𝒅𝒙 = 𝟏
𝟐𝒏𝝅𝒙 𝑳
𝑨𝟐 𝒔𝒊𝒏( 𝑳 ) 𝑨𝟐
or [𝒙 − 𝟐𝒏𝝅 ] =𝟏 ⟹ [(𝑳 − 𝟎) − (𝟎 − 𝟎)] = 𝟏
𝟐 𝟐
𝑳 𝟎

𝑨𝟐 𝑳 𝟐
or =𝟏 ⇒𝑨=√ --------- (11)
𝟐 𝑳

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From eqn’s (9) and (11), we get,
𝟐 𝒏𝝅𝒙
𝝍𝒏 (𝒙) = √ 𝒔𝒊𝒏 ( ) ----------- (12)
𝑳 𝑳

Eqn.(12 represents the probability amplitude of the particle in nth level of the given potential
region.
Calculation of Energy of the particle:
From equations (3) and (8), we have,
2𝑚𝐸 𝑛𝜋
= 𝑘 2 (since, 𝑘 = )
ℏ2 𝐿

𝟐𝒎𝑬 𝒏 𝟐 𝝅𝟐 𝒏 𝟐 𝝅𝟐 ℏ 𝟐
Hence, = ⟹ 𝑬=
ℏ𝟐 𝑳 𝟐
𝟐𝒎𝑳𝟐

𝒏𝟐 𝒉𝟐 ℎ
𝑬𝒏 = (𝑠𝑖𝑛𝑐𝑒, ℏ = 2𝜋) ------ (13)
𝟖𝒎𝑳𝟐
where n is the positive Integer.
Eqn. (13) represents the energy of the
particle for each value of n. The wave function
of this energy level is given in eqn. (12). Therefore
the particle in the box can have discrete values of
energies. These values are quantized. Note that the
particle cannot have zero energy .The normalized
wave functions Ψ1, Ψ2, Ψ3 given by eqn. (12) is
plotted. The values corresponding to each En value is
known as Eigen value and the corresponding wave
function is known as Eigen function.
The wave function Ψ1, has two nodes at x = 0 & x = L.
The wave function Ψ2, has three nodes at x = 0, x = L/2 & x = L.
The wave function Ψ3, has three nodes at x = 0, x = L/3, x = 2L/3 & at x = L.
CONCEPT OF POTENTIAL BARRIER (TUNNELING EFFECT):
➢ To understand the phenomenon, particles attempting to travel between potential barriers can be
compared to a ball trying to roll over a hill.
➢ Classical mechanics predicts that particles that do not have enough energy to classically
surmount a barrier and will not be able to reach the other side. Thus, a ball without sufficient

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 energy to surmount the hill would roll
back down. Or, lacking the energy to
penetrate a wall, it would bounce back
(reflection) or in the extreme case,
bury itself inside the wall
(absorption).
➢ In quantum mechanics, these particles
can, with a very small probability,
tunnel to the other side, thus crossing
the barrier.

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