lOMoARcPSD|24001846

Unit-1 (Quantum mechanics)

Engineering Physics (Galgotias University)

Studocu is not sponsored or endorsed by any college or university

Downloaded by Neha Bharti ([email protected])
 lOMoARcPSD|24001846

Module-1: Quantum physics

8 Lecture hours
Dual Nature of Electro-magnetic radiation (Wave-Particle duality), de-Broglie waves, Davisson &
Germer’s Experiment (Experimental verification of de-Broglie waves), Heisenberg Uncertainty Principle
and its Applications, Schrodinger’s wave equations, Particle in a Box

Classical Physics and its limitations: At the end of 19th century, physics consists of Newtonian
classical mechanics (used to predict dynamics of material bodies) and Maxwell’s electromagnetic
theory (to study radiation: matter and radiation were described in terms of particles and waves
respectively). The interaction between matter and radiation were described by Lorentz force and /or
by thermodynamics. At the turn of 20th century, classical physics were challenged at two fronts:
(1) Relativistic domain: Einstein’s theory of relativity showed that Newtonian classical mechanics
fails at speeds comparable to that of light.
(2) Microscopic domain: At microscopic level, validity of classical physics ceases and new concepts
are required to describe, for instance, the structure of atoms and molecules and how light interact with
them. Some of the important physical phenomena which could not be explained by classical physics
are:
Blackbody Radiation: Any object with a temperature above absolute zero emits light at all wavelengths. If
the object is perfectly black (so it doesn't reflect any light), then the light that comes from it is called
blackbody radiation. The energy of blackbody radiation is not shared evenly by all wavelengths of light.
The spectrum of blackbody radiation (below) shows that some wavelengths get more energy than others.
The radiated energy can be considered to be produced by standing wave or resonant modes of the cavity
which is radiating. The amount of radiation emitted in a given frequency range should be proportional to
the number of modes in that range. The best of classical physics suggested that all modes had an equal
chance of being produced, and that the number of modes went up proportional to the square of the
frequency (Rayleigh and Jeans law). But the predicted continual increase in radiated energy with
frequency (called the "ultraviolet catastrophe") did not happen experimentally. To explain the observed
behaviour, Planck in 1900 proposed that energy exchange between radiation and matter takes place in
discrete or quantized amounts. If ν is the frequency of radiation, the energy exchange occurs in steps of hν,
which he called energy of a quantum, where h is a fundamental constant called the Planck’s constant. Using
this idea, Planck gave a successful explanation of black body radiation.

2. The Photoelectric Effect: When light shines on the surface of a metallic substance, electrons in the
metal absorb the energy of the light and they can escape from the metal's surface. This is called the
photoelectric effect. Using the idea that light is a wave with the energy distributed evenly throughout the
wave, classical physics expected that when using very dim light, it would take some time for enough light
energy to build up to eject an electron from a metallic surface. Experiments show that if light of a certain
frequency can eject electrons from a metal, it makes no difference how dim the light is. There is never a
time delay. In 1905, Albert Einstein came up with the solution. Using Planck's idea, Einstein postulated that
light must consist of a stream of quanta of energy. Each quantum of light energy is called a photon and each
photon has an energy equal to hν (Planck's constant times the frequency of the light). Therefore the energy
of light is not evenly distributed along the wave, but is concentrated in the photons. A dimmer light means
fewer photons, but simply turning down the light (without changing its frequency) does not alter the energy
of an individual photon. So for a specific frequency light, if a single photon has enough energy to eject an
electron from a metallic surface, then electrons will always be ejected immediately after the light is turned
on and the photons hit the metal.

3. The Hydrogen Atom: When a small tube of hydrogen gas is heated, it begins to glow and emit light.
Unlike the blackbody radiation that comes from a hot dense solid or gas, this light consists of just a few
colours (wavelengths). Hydrogen consists of a positively charged proton at the centre, with a negatively
charged electron orbiting around it. The electrical attraction between the positive proton and the negative
electron keeps the electron in orbit. Classical physics said that because the orbiting electron is constantly
changing direction, it should emit electromagnetic radiation. As a result, the electron should be continually
losing energy. In fact, physicists calculated that the electron should lose all of its energy and spiral down
into the proton in only about 0.000000000001 second! In other words, atoms should not exist longer than a
Page 1 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

mere 10-12 seconds. Thus the stability of atom cannot be explained classically.To explain the stability of
atom, Bohr postulated that atoms can be found only in discrete energy states and the interaction between
atoms and radiation i.e., the emission or absorption of energy can only occur in discrete amounts of hν
because it results from transitions between its discrete energy states.

Development of Quantum mechanics: After a series of breakthroughs by Planck, Einstein and Bohr,
Compton in 1923, gave the most conclusive evidence of particle nature of radiation. the scattering of X-
rays with electrons, he confirmed that x –rays behave like particles with momenta hν/c; where ν is the
frequency of the X –rays. Further in 1923, de Broglie postulated that material particles themselves exhibit
wave nature. This concept was experimentally verified by Davisson and Germer; they showed that
interference patterns, a property of waves, can be obtained with material particles like electrons. Quantum
mechanics was developed as a theory later by Hesienberg and Schrodinger independently in 1925 and
1926. Thus quantum mechanics is the theory that describes the dynamics of matter at the microscopic scale.

Dual nature of matter and radiation:Till the end of 19th century, matter and radiation were identified as
two distinct identities characterised by mutually exclusive properties. Matter was thought to have particle
nature while radiation was said to exhibit wave nature. While the full description of a particle requires only
one parameter, the position vector r(t), waves can be described by wave functions which have two
parameters, the amplitude and the phase. Particles are characterised by an energy E and momentum p while
waves by an amplitude and a wave vector k (|k|=2π/λ). Classically, waves exhibit interference patterns,
particles do not. However at the start of 20 th century, classical physics failed to explain several experimental
findings for radiation. This includes spectral energy distribution of black body radiation, photoelectric
effect and Compton Effect. These phenomena involved interaction of matter and radiation at the
microscopic level and can only be explained by particle nature of radiation. Thus it was postulated that
radiation (light) consists of small particles with discrete energies i.e. quanta. However phenomena like
interference, diffraction, polarization etc can only be explained when wave nature of radiation is
considered. Thus it is evident that radiation has dual nature i.e. it can behave like particles as well as like
waves. Similarly electrons and other microscopic particles were found to possess both wave and particle
nature. The wave nature of matter was postulated by de Broglie and was experimentally verified by
Davission-Germer and Thomson (electron diffraction). Thus matter also possesses dual nature. This dual
nature of matter can never be reconciled within the context of classical physics, however quantum
mechanics provides a proper framework that reconciles the particle and wave aspects of matter. By using a
wave-function to describe microscopic particles, quantum mechanics can simultaneously describe the wave
and particle aspects of microscopic systems.

A short introduction to Relativistic formulae:

(1) Mass: When a particle is moving with a velocity v, which is comparable to speed of light (c = 3x 10 8
1
m=γ m 0 , where γ =

m/s), its mass (m) does not remain constant and is given by √ 1−
v2
c2

The mass of a particle at rest i.e. v=0 is called rest mass (m 0).

(2) Momentum:
p=mv=γ m0 v

(3) Energy: E=mc2 =γ m 0 c2 , Rest energy E0 = m0 c2

(4) Kinetic energy KE=E−E0 =mc 2 −m0 c 2 =( γ −1) m0 c 2

2 2 2 2 4
(5) Relation between E and p: E = p c + m0 c

Note: Photon is a special particle with zero rest mass i.e. m 0=0, so E=pc for a photon.

Page 2 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

WAVES: A wave is a disturbance or oscillation that travels through space accompanied by a transfer of
energy. The most basic wave form is a harmonic wave which can be represented by

y= A cos(ωt−kx )
2π
where ω=2 πυ is the angular frequency and υ is the frequency , k= is the wavenumber .
λ

If vp is the phase velocity or wave velocity of the above wave moving in +ve X-direcion, then
v p = λυ .

x
y= A cos 2 πυ(t− )
Thus the above equation can also be written as
vp

de Broglie’s hypothesis and Matter waves:

In 1923, de Broglie proposed that the wave particle duality must not be restricted to radiation but should be
universal i.e. matter particles should also possess wave particle duality. He proposed that the wavelength
h
λ=
associated with a particle with momentum p is given by p . This relation, called de Broglie
relation, connects the momentum of the particle with its wavelength.

Page 3 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

(f) Relativistic case: When a charge particle carrying a charge q is accelerated by potential difference V
2 2 2 2 2 4 2 2
volts, then its energy is E=qV +m0 c and also E = p c +m0 c =( qV +m 0 c )

⇒ p2 c2 +m 20 c 4 =(q2 V 2 +2 qVm0 c 2 +m 20 c 4 )⇒ p2 c 2=q 2 V 2 +2 qVm 0 c 2

⇒ p2 =
q2 V 2 +2 qVm0 c 2
c2
⇒ p=
√ q 2 V 2 +2 qVm 0 c 2
c 2
√
= 2 qVm0 1+
( qV
2 m0 c 2 )
h h
λ= =

√
p
2 qVm0 1+
( qV
2m0 c2 )
(g) Wavelength of a particle with rest mass m0 and kinetic energy K for relativistic case:

2 2 2
As E = p c + m0 c
2 4
and
Kinetic energy=K=E−E0 =E−m0 c 2 =√ p 2 c 2 +m 20 c 4 −m0 c 2

⇒ K +m0 c 2= √ p2 c 2 +m20 c 4 ⇒( K +m0 c 2 )2 =p 2 c 2 +m20 c 4 ⇒ K 2 +2 Km 0 c 2 +m20 c 4 = p2 c2 +m 20 c 4

2 2
⇒ K +2 Km 0 c = p c 2 2
⇒ p=
√ K ( K +2 m0 c 2 ) h
⇒ λ= =
hc
p √ K ( K +2 m c 2 )
c 0

Page 4 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

Properties of Matter Waves:

1. Lighter the particle, greater is the wavelength associated with it.

2. Smaller the velocity of the particle, greater is the wavelength associated with it. When v = 0 then λ = ∞ ,
i. e., wavelength becomes indeterminate and if v = ∞ then λ = 0. This shows that matter waves are
associated with particles in motion. These waves are produced whether the particle is charged or
uncharged. This implies that these waves are not electromagnetic.
3. The quantity whose variation makes up matter waves is the wave function (ψ). The value of the wave
function associated with a moving body at any point (x,y,z) in space at any time (t) is related to the
probability of finding the body there at that time. Since the magnitude of ψ oscillates between positive and
negative values, the wave function ψ has no physical significance as probability of finding the particle at
2
any place at any instant cannot be negative. However |ψ| is always positive and thus is physically
2 2
significant. Max Born in 1926 interpreted |ψ| as the probability density i.e. |ψ| dxdydx gives the
probability of finding the particle at a time t in the volume element dxdydz in space. If we integrate
over the entire space, we are certain that the particle is somewhere in it. Thus the total probability of
finding the particle somewhere in the space must be equal to 1.
∫ |ψ|2 dxdydz=1
i.e., all space .
4. Wave velocity (or phase velocity) of de Broglie waves:
As the wave velocity (vp) of any wave is related to frequency (ν) and wavelength (λ) as
v p = λν
Further the energy is related to frequency of a wave as E=hν , For a particle with rest mass m0 and
2 2
velocity V , the energy is given by E=mc =γ m 0 c . Thus for the wave associated with this particle,
2
γ m0 c
E=mc 2 =γ m0 c2 =hν ⇒ ν=
h , The wavelength of this wave is given by de Broglie’s relation
h h
λ= =
i.e.,
p γm0 V , Therefore putting the values of λ and ν in
v p = λν gives
2
h γ m0 c c 2
c
2
v p = λν=( )( )= v p=
γm0 V h V , Thus V , since the particle velocity is always less than the
velocity of light (c), so RHS of this equation is greater than c. Thus,
v p >c . Hence the de Broglie
wave associated with a particle cannot be described by a single wave.

Wave packet: As the particle velocity V is less than c and the wave velocity of de Broglie wave comes
out to be greater than c. This means that the de Broglie wave associated with the particle would travel much
faster than the particle itself and would leave the particle far behind. This is physically inconsistent and
hence it is clear that a single wave cannot be used to describe a moving particle. Instead a moving particle
can be represented by superposition of a group of waves slightly differing in velocity and wavelength,
with phases and amplitude such that they interfere constructively over a small region of space where the
particle can be located and outside this space they interfere destructively so that the amplitude reduces to
zero. Such a group of waves is called a wave packet.
Consider two wavs having same amplitude A but slightly different angular frequencies (ω and ω+dω ) and
wave numbers ( k and k+dk ). These waves can be represented as
y 1 =A cos(ωt −kx ) and y 2 =A cos[(ω +dω )t−(k +dk ) x ]
When these two waves interfere the resultant is given by
y= y 1 + y 2= A cos (ωt−kx )+ A cos [(ω+dω )t−(k +dk ) x ]
ωt−kx +(ω+dω )t−( k+dk )x ωt−kx−[(ω+dω )t−(k +dk ) x ]
¿ 2 A cos [ ]cos[ ]
2 2
(2 ω+dω )t−(2 k +dk ) x dω t−dk x ]
¿ 2 A cos [ ]cos [ ]
2 2
since dω and dk are very small, so 2ω + dω ~ 2ω and 2k + dk ~2k.
Page 5 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

(2 ωt−2 kx ) dω t−dk x ] dω t−dk x

y=2 A cos[ ]cos[ ]=2 A cos(ωt−kx)cos( )
Thus 2 2 2
The above equation represents a wave of 2 A cos(ωt−kx) with a modulation (envelope) of
dω t−dk x
cos( )
2 . The velocity of first part is the wave velocity or phase velocity (vp) while that of the
ω dω
v p= and v g =
envelop is called the group velocity (vg). Thus k dk . The figure below shows the
wave packet formed by superposition of two waves
ψ 1 and ψ 2 .

Relation between particle velocity ( V) and group velocity (vg): The wavelength of this wave is given by
h h
λ= =
de Broglie’s relation i.e.,
p γm0 V . The wave velocity (v ) of any wave is related to its frequency
p
2
h γm0 Vv p γm0 c c
2
v p= ν ⇒ ν= = v p=
(ν) and wavelength (λ) as p
v = λν . Thus γm 0 V h h , as V
2
γm0 c 2 πγ m0 c 2 2 π 2 πp 2 πγ m 0 V
ν= ⇒ ω=2 πν= ……(1) k= = = ……(2)
Thus h h and λ h h
dω dω/ dV
v g= =
dk dk / dV , Now we will find dω /dV and dk /dV .
2
2 πγ m0 c
d( )
dω h 2 πm0 c 2 dγ
= = . . .. .. .. . .. .. . .. .. .( 1 )
dV dV h dV
dγ d 1 V
= ( )= 2
dV dV √ 1−V /c
2 2
c (1−V 2 /c 2 )3/2
2 πγ m0 V
d( ) 2 πm
dk h 0 d (γV )
= = .. . .. .. . .. .. . .. .. . .( 2)
dV dV h dV
d (γV ) c3
= 2 2 3 /2
dV (c −V )

2 πm 0 c2 dγ dγ V
c2 c2 2
dω dω/ dV h dV dV c (1−V 2 / c2 )3/2
v g= = = = = =V
dk dk / dV 2 πm 0 d ( γV ) d ( γV ) c3
h dV dV (c 2 −V 2 )3/ 2

Page 6 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

dω
v g= =V
Thus, dk , i.e. the group velocity is equal to the particle velocity. Hence a moving particle can
be described using a wave packet.

Relation between group velocity and phase velocity in a dispersive medium:

In a dispersive medium wave velocity or phase velocity is frequency dependent.

Davisson & Germer’s electron diffraction experiment:

In 1927, Davisson & Germer were studying the scattering of electrons from a Nickel block. Electrons from
an electron gun were allowed to incident on a Nickel target and after scattering, the electrons are collected
using an electron detector which can be moved along a circular scale. This experiment was being carried
out in an evacuated chamber as shown in the figure 1. In the midst of their work an accident occurred and
air entered their apparatus which oxidised Nickel. To reduce the oxide back to pure Nickel, the target was
baked in a hot oven. Because of this heat treatment nickel crystallized. For different values of potential the
electrons were collected at different positions. The current which is the measure of the intensity of the
diffracted beam, is plotted against the diffraction angle Φ for each accelerating potential. Typical polar
graphs of electron intensity are shown in the Figure 2.The method of plotting is such that the intensity at
any point is proportional to the distance of the curve from origin. Classical physics predicted that the
scattered electrons will emerge in all directions with only a moderate dependence of their intensity on
scattering angle and even less on their energy. However they found quite different results. Instead of a
continuous variation of intensity with angle, distinct maxima and minima were observed whose positions
were dependent on electron energy. This confirmed that electrons are showing diffraction and thus showing
wave nature. This experiment thus confirmed the de Broglie hypothesis.

Figure 1: Experimental set up

Page 7 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

Figure 2: Polar plots of scattered intensity at various accelerating potentials.

Let us try to estimate the wavelength associated with electrons using the results of this experiment and
compare it with the de Broglie hypothesis. It was observed that up to a voltage of 40 volts, the intensity
variation of scattered electrons follows a smooth and a bump begins to appear in the curve at an
accelerating voltage of 44 volts. As the potential difference is further increased, the bump becomes sharper
and is most prominent at 54 volts electrons at Φ = 50 0. Beyond 54 volts the bump gradually diminishes and
become insignificant at 68 volts electrons. According to de Broglie, the wavelength associated with
electron accelerated through a potential V is given by

From X-ray analysis, it is known that nickel crystal acts as plane diffraction grating with grating space
d = 0.91 Ǻ. In this case we observe a maxima at Φ = 50 0. The corresponding angle of incidence relative to
the family of Bragg planes as shown in the figure is

This is in good agreement with the wavelength computed from de Broglie hypothesis. Hence, the
de Broglie’s concept of matter waves is confirmed.

Heisenberg’s Uncertainty Principle: As a moving particle exhibits dual nature i.e., wave nature as well as
particle nature; there arises a fundamental limit to the accuracy with which one can measure its position
and momentum simultaneously. If the wave group is more localised, i.e., the position is well defined, its
wavelength (λ) cannot be defined precisely. In turn the momentum (p=h/λ) is not well defined. On the other
hand, if the wave group is spread out, the wavelength can be better defined and hence the momentum can
be measured accurately. But the position will not be well defined as the wave packet is more spread out.
Thus it is impossible to measure the position and momentum simultaneously with accuracy. Heisenberg
pointed out this fact in 1927 which is a consequence of wave particle duality. In its original form,
Heisenberg’s Uncertainty Principle states that: If the x-component of the momentum of a particle is
measured with an uncertainty ∆px, than its x-position cannot be measured more accurately than
∆x = ћ/(2∆px). The three dimensional form of the uncertainty relations for position and momentum can be
ℏ ℏ ℏ
Δx Δp x≥ ; Δy Δp y≥ ; Δz Δp z ≥
written as 2 2 2

Page 8 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

Heisenberg’s Uncertainty Principle can be generalized to any pair of complementary or canonically

conjugate dynamical variables: It is impossible to devise an experiment that can measure simultaneously
two complementary variables to arbitrary accuracy. Examples of complementary or canonically conjugate
dynamical variables are Energy and time, angular momentum and angular displacement etc.
Thus uncertainty principle ensures that unlike classical physics which is deterministic, quantum mechanics
is a completely in-deterministic theory.
The relationship between ∆x and ∆px, depends on the shape of the wave packet which represents the
particle. It has been found that Gaussian wave packet is the least uncertainty packet for which
1
Δx Δk= ;
2 Here Δk is the uncertainty in the wave number. Thus in general we can write:
1 2π 1 2 πp x 1
Δx Δk≥ ⇒ Δx Δ( )≥ ⇒ Δx Δ( )≥
2 λ 2 h 2
px 1 ℏ
⇒ Δx Δ( )≥ ⇒ Δx Δp x ≥
ℏ 2 2
p2 2 p Δp
E= x ⇒ ΔE= x x =v x Δp x ; Now Δx =v x Δt
In terms of energy and time, 2m 2m
Δx ℏ
ΔE= Δp x ⇒ ΔEΔt=ΔxΔp x ≥
This gives Δt 2
ℏ
ΔE Δt≥
Thus 2
It has to be noted that these uncertainties are not because of inadequate apparatus but because of the
wave particle duality. Any errors in measurement will also increase the uncertainty.

Applications of Heisenberg Uncertainty Principle:

1. Non-Existence of electrons in the nucleus: The diameter of nucleus is of order 10 -14 m. Therefore the
uncertainty (∆x) in the position of any particle inside the nucleus will be of order 10 -14 m. So the
uncertainty in momentum will be ∆px = ћ/(2∆x) = 0.527 X 10-20 kg m/s. If uncertainty in momentum is of
this order, the momentum itself will be of same order. i.e., p ~ 0.527 X 10 -20 kg m/s
For an electron, the rest energy E0 = m0c2 = 511 keV
Value of pc for electron is 9.88MeV which is much greater than E 0. This means that we have to follow
2 2 2 2 4
relativistic approach. Thus using E = p c +m0 c , the total energy comes out to be ~10MeV. If an
electron exists inside the nucleus, it should come out with at least 10 MeV. But we know that during beta
decay, electrons emitted have energies only of order 3 to 4 MeV. Thus it can be concluded that an electron
cannot exist inside a nucleus.

For protons or neutrons, m0 = 1.67 x 10-27 kg. So E0 = m0c2 ~900 MeV, whereas pc ~ 9.88 MeV. Thus this is
a non- relativistic case. So E = p2/2m =52 KeV. This energy is much less than the energies of particles
emitted by nucleus. Hence protons, neutrons and other heavy particles can exist inside the nucleus.
2. Radius of Bohr’s First orbit: To estimate the radius of Bohr’s first orbit, we will assume that the radius
is of same order as the uncertainty in position; velocity and momentum of electron are of same order as the
uncertainty in velocity and momentum. i.e., Δx ~ x , Δp~ p and Δv ~ v .
ℏ ℏ
Δx Δp≥ ⇒ Δx Δp ~ ℏ⇒ Δp=
From Heisenberg’s Uncertainty Principle, 2 Δx
The kinetic energy (K) and the potential energy (U) are given by
1 p2 ( Δp)2 ℏ2 1 Ze 2
K= mv 2 = ⇒ ΔK = ~ , U =−
2 2m 2m 2( Δx )2 4 πε 0 Δx
2 2
ℏ 1 Ze
E=K +V = −
Total energy is 2( Δx )2 4 πε 0 Δx

Page 9 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

For the first orbit, E should be minimum i.e.,

2
dE dE d ℏ2 1 Ze 2 4 πε 0 ℏ
= =0 ⇒ [ 2
− ]=0 ⇒ Δx= 2
dx dΔx dΔx 2( Δx ) 4 πε 0 Δx mZe
d2 E 4 πε 0 ℏ2
2
= positive at Δx= 2
We confirm that d Δx mZe
2
4 πε 0 ℏ
Δx= 2
Hence a rough estimate of Bohr’s first orbit is mZe which gives 5.3 nm for Z=1. The energy of
electron at this orbit comes out to be E ~ -13.6 eV. These numbers match very close to actual observed
energies!!

Wave Function: A wave function is a complex function which contains all the information about a
quantum system and from which all the dynamical physical quantities such as linear momentum, angular
momentum and energy of the system can be computed. The value of the wave function associated with a
moving body at any point (x,y,z) in space at any time (t) is related to the probability of finding the body
there at that time. Since the magnitude of ψ oscillates between positive and negative values, the wave
function ψ has no physical significance as probability of finding the particle at any place at any instant
cannot be negative.
2
However |ψ| is always positive and thus is physically significant. It gives the probability density
2
i.e. |ψ| dxdydx gives the probability of finding the particle at a time t in the volume element dxdydz
in space.

Being a complex function, the wave function ψ can be written as

2 2 2
ψ= A+iB , |ψ| =ψψ∗¿( A +iB)( A−iB)=A +B
Normalization: If we integrate over the entire space, we are certain that the particle is somewhere in it.
Thus the total probability of finding the particle somewhere in the space must be equal to 1.
+∞
∫ |ψ| dxdydz=1⇒ ∫ |ψ| dxdydz=1
2
−∞
2

i.e., all space . This condition is called the normalization condition and
the wave function which satisfies this condition is called a normalized wave function.

For a wave function to be physically meaningful following conditions need to be satisfied:

(1) ψ must be continuous and single valued.
(2) The derivative of ψ must be continuous and single valued.
+∞

(3) ψ must be normalizable i.e. −∞

∫ |ψ| dxdydz=1
2
. For this condition to satisfy, ψ must go to zero as
x →±∞ , y →±∞ , z→±∞

Wave Equation: The classical differential equation representing the wave motion is given by
∂2 y 1 ∂2 y
=
∂ x 2 v 2 ∂t 2
p , where vp=wave velocity and y is the variable which varies as the wave propagates in x
direction. For example, for standing waves in a stretched string it can be displacement, in a sound wave it is
pressure and in an electromagnetic wave it is electric field and magnetic field.
−iω( t− x/v p )
The general solution of this equation is given by y= Ae =Ae−i( ωt−kx )

Schrodinger’s equation: It is a basic physical principle that cannot be derived from anything else.
In quantum mechanics, ψ corresponds to the wave variable y of the wave motion in general. However, ψ,
unlike y, is not itself a measurable quantity and may therefore be complex. Taking analogy from wave
motion, we assume that ψ for a free particle moving freely in +X direction can be given by:

Page 10 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

−iω( t−x / v p )
ψ= Ae = Ae−i( ωt−kx )
Schrodinger’s equation is the fundamental differential equation for ψ, which can be solved to get ψ in a
specific situation. This equation can be arrived at in various ways, but it cannot be rigorously derived
from existing physical principles: the equation represents something new.

Schrodinger time dependent wave equation: We assume that ψ for a particle moving freely in +X
−iω( t−x / v p )
direction can be given by: ψ= Ae = Ae−i( ωt−kx )
2 πE E h 2π 2π p
E=hυ and ω=2 πυ= = ; Further λ= and k= = =
Now we know that h ℏ p λ h/p ℏ
E p i
−i( ωt−kx ) −i( ℏ t− ℏ x ) − ℏ ( Et − px)
Thus, ψ= Ae =Ae = Ae , where E = energy and p = momentum of the particle.
i
− ℏ ( Et −px )
ψ= Ae ⋯⋯(1 )
Taking partial derivative w.r.t x, we get

i i
∂ψ − ( Et− px) ip − ( Et − px) ip ∂ψ ip
=A ∂ e ℏ =A ℏ e ℏ =ℏψ ⇒ = ψ ⋯⋯(2)
∂x ∂x ∂x ℏ
Further taking double derivative w.r.t x, we get
2
∂ ψ ∂ ip ip ∂ψ ip ip − p2 ∂ ψ
2
= ( ψ )= = ψ = ψ ⇒ p2 ψ =−ℏ 2 ⋯⋯(3)
∂2 x ∂ x ℏ ℏ ∂x ℏ ℏ ℏ2 ∂2 x
Taking partial derivative w.r.t time t, we get
i i
∂ψ − ( Et− px) −iE − ( Et − px) −iE −ℏ ∂ψ ∂ψ
=A ∂ e ℏ =A ℏ e ℏ = ℏ ψ ⇒ Eψ= =i ℏ ⋯⋯(4 )
∂t ∂x i ∂t ∂t
For a non relativistic particle, using energy conservation, total energy (E) is the sum of K.E. (=p2/2m) and
2
p
E= +U
potential energy (U) i.e., 2m , Associating ψ to both sides of this equation we get,
2
p ψ
Eψ= +Uψ
2m
Putting the values of E ψ and p2 ψ from (3) and (4), we get
2 2
∂ ψ −ℏ ∂ ψ
iℏ = +Uψ
∂t 2m ∂2 x
For a free particle U=0 or constant. In general the when potential energy depends on both x and t
2 2
∂ ψ −ℏ ∂ ψ
iℏ = +U ( x ,t )ψ
∂t 2m ∂ 2 x
The above equation is known as the time dependent Schrodinger’s equation (TDSE) in one dimension. In
three dimensions, the above equation can be written as

2
∂ ψ −ℏ2 ∂2 ψ ∂2 ψ ∂2 ψ
=
2
iℏ
2
+ +
∂t 2m ∂2 x ∂2 y ∂2 z [
+ U (x , t )ψ
,
]
∂ψ ∂ψ ∂ψ
2
+ 2 + 2 =∇ 2 ψ
Here ∂ x ∂ y ∂ z is called Laplacian of ψ. Thus

2
∂ ψ −ℏ 2
iℏ = ∇ ψ + +U (x , t )ψ
∂t 2m
2 2 2
∇ 2 = ∂2 + ∂2 + ∂2
∂ x ∂ y ∂ z is known as the Laplacian operator.
Time independent Schrodinger’s equation (The steady state form of Schrodinger’s equation):
Page 11 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

When the potential energy does not vary explicitly with time i.e. U(x,t)= U(x), Schrodinger’s equation can
be simplified by removing all reference to time.
We start with the wave function ψ(x,t) for a particle moving freely in +X direction :
i i i i i
− ℏ ( Et − px) ℏ px − ℏ Et − ℏ Et ℏ px
ψ ( x, t )= Ae =Ae e =ψ ( x) e , where ψ ( x)= Ae
Here ψ(x) represents the part of wave function which depends only on position and is independent of
time (t). The time dependent Schrodinger’s equation (TDSE) in one dimension is
2 2
∂ ψ −ℏ ∂ ψ ∂ψ i
iℏ = +U ( x ,t )ψ Eψ=i ℏ − ℏ Et
∂t 2m ∂ 2 x , Putting ∂t , U(x,t)= U(x) and ψ ( x, t )=ψ ( x ) e , we
get

(ψ( x ) e ) +U ( x)ψ( x) e
i
− ℏ Et
i 2 ∂2 i
− ℏ Et −ℏ − ℏ Et
Eψ (x ) e =
2m ∂2 x
i 2 i i
−ℏ − ℏ Et ∂ ψ ( x )
2 2 2
− ℏ Et − ℏ Et −ℏ d ψ
⇒ Eψ ( x ) e = e + U ( x )ψ (x ) e ⇒ Eψ ( x ) = +U ( x )ψ (x )
2m ∂2 x 2 m dx 2
∂2 ψ ( x ) d 2 ψ
= 2
We have taken ∂2 x dx as ψ(x) depends only on x, so partial derivative is equal to the total
derivative. The above equation can be written as
2
d ψ 2m
+ ( E−U ( x ) ) ψ ( x )=0
dx 2 ℏ2
This is the time independent Schrodinger’s equation in one dimension. The three dimensional time
independent Schrodinger’s equation can be written as
2m
∇2 ψ + ( E−U ( x ) ) ψ ( x )=0
ℏ2
2 2 2
∂ ψ ∂ψ ∂ψ
2
∇ ψ= 2 + 2 + 2
Here ∂ x ∂ y ∂ z is called Laplacian of ψ.
The values of energy for which time independent Schrodinger’s equation can be solved are called energy
Eigen-values and the corresponding wave functions are called Eigen-functions. The above equation can
be written as
−ℏ 2 2
Eψ (x ) = ∇ ψ +U (x )ψ ( x ) =Hψ( x )
2m Or Hψ( x ) =Eψ (x )
2
−ℏ 2
H= ∇ +U ( x )
Here 2m is called Hamiltonian operator and Hψ( x ) =Eψ (x ) is called eigen-
value equation.

Particle in a One-Dimensional Box with infinitely hard walls (InfinitePotential Well)

Consider a particle of mass m moving along x-axis between the two rigid walls x=0 & x=L. The particle is
free to move between the walls. The potential energy of the particle between the two walls is zero and no
force is acting on the particle. The particle does not loose energy when it strikes back and forth in the
potential well because the walls are infinitely rigid. Let U(x) is the potential energy function. Then U(x) can
be represented mathematically as U(x) = 0 for 0 < x < L
U(x) =  for x  0 and x  L

Page 12 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

The wave function for the particle can be determined by solving the Schrodinger equation, i.e.
d ψ 2m( E−U )
2
+ ψ=0
dx 2 ℏ2
Since U=0 inside the box, we get
2
d ψ 2mE
+ 2 ψ =0
dx 2 ℏ
The general solution of this equation is ψ ( x )= A sin( kx)+B cos(kx )
Where A and B are arbitrary constants to be determined from the boundary conditions and k is given by

k=
√ 2 mE
ℏ2 . The boundary conditions are ψ(x) = 0, at x = 0 and at x = L.

For x = 0, ψ ( x )= A sin( kx )+B cos(kx )⇒ B=0

Thus the wave function becomes ψ n =A sin(kx )
Further ψ(x) = 0, at x = L gives
sin(kL )=0 ⇒ kL=nπ
Since A cannot be zero as this will make the wave function zero everywhere.
nπ
k=
, n=1 , 2 , 3 etc
L

The wave function becomes

ψ n =A sin
nπ
L
x ( )
The subscript n in ψn means that the wave-function depends on n. The allowed energies are obtained using

k=
nπ
L
n2 π 2 2 mE n2 π 2
⇒k 2= 2 ⇒ 2 n = 2 ⇒ En =
L ℏ L
ℏ2 nπ 2
2m L ( )
( )
2 2
ℏ nπ
En = ⇒ E n ∝n2
2m L
Each value of the energy E n for n=1, 2, 3 etc is called an energy Eigen value and corresponding wave
function is called Eigen function. Thus inside the box, the particle can only have the discrete energy
values. The allowed wave functions and the allowed energy values E n exist only for integral values of n.
The number n is called the quantum number. Hence energy spectrum consists of discrete energy levels
where the spacing between the levels is determined by the values of n and L.

Wave Functions: The constant A can be determined by using this information that the probability of
finding an electron somewhere inside the box is unity, i.e.
L

∫ ψ n ψ n dx=1
¿

0
This is called as normalisation condition. We get,
L L L
A ∫ sin
2

0
nπ
L
2
( )
x dx =1⇒ A 2∫ 1−cos
0
2nπ

Thus the normalized wave function is given by

L
x dx=2 ⇒ A2 ∫ dx=2
0
( ) ⇒ A=
√ 2
L

Page 13 of 14

Downloaded by Neha Bharti ([email protected])

 lOMoARcPSD|24001846

ψ n=
√ 2
L
sin
nπ
L
x ( )
The energy levels and the wave functions corresponding to n=1, 2, 3, and 4 are shown below;

The probabilities of finding the particle are given by |ψ|2 and are shown below for first three wave
functions.

Particle in a box with finite walls (Finite potential well): When the potential is finite, there is a
probability associated with the particle being found outside the box. Classically, if the total energy of the
particle is less than potential energy barrier of the walls it cannot be found outside the box. In quantum
mechanics, there is a non-zero probability of the particle being outside the box even when the energy of the
particle is less than the potential energy barrier of the walls. Thus the wave function is non zero even
outside the box as shown below.

Page 14 of 14

Downloaded by Neha Bharti ([email protected])