AMC ENGINEERING COLLEGE

DEPARTMENT OF PHYSICS

Module 2 Notes

Quantum Mechanics

I/II SEMESTER Applied Physics for CSE Stream

Subject code: 22PHYS12/22
Contents

1 Quantum Mechanics 3
1.1 Wave-Particle Duality . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 de Broglie’s Hypothesis . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Wave Packets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.1 Phase Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.2 Group Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Heisenberg’s Uncertainty Principle . . . . . . . . . . . . . . . . . . . . 10
1.3.1 Principle of Complementarity . . . . . . . . . . . . . . . . . . . 11
1.3.2 Non-existence of electron in the nucleus of an atom (non-relativistic
case) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4 Wavefunction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4.1 Properties of a wavefunction . . . . . . . . . . . . . . . . . . . . 13
1.5 Schrodinger’s Time-Independent Wave Equation . . . . . . . . . . . . . 13
1.5.1 Particle in an infintely deep potential well (Particle in a 1D box) 18
Chapter 1

Quantum Mechanics

Syllabus
Quantum Mechanics
de Broglie Hypothesis and Matter Waves, de Broglie wavelength and derivation
of expression by analogy, Phase Velocity and Group Velocity, Heisenberg’s Uncer-
tainty Principle and its application (Non existence of electron inside the nucleus
- non relativistic case), Principle of Complementarity, Wave Function, Time inde-
pendent Schrödinger wave equation (Derivation), Physical Significance of a wave
function and Born Interpretation, Expectation value, Eigen functions and Eigen
Values, Particle inside one dimensional infinite potential well, Quantization of En-
ergy States, Waveforms and Probabilities. Numerical Problems.

1.1 Wave-Particle Duality

Light (radiation) appears to behave as a wave in some scenarios and as a particle in
other scenarios.
A particle has mass; it occupies space; it can move from one place to another; it
gives energy when slowed down or stopped. Thus the particle can be specified by mass,
velocity, momentum, energy. And any two particles cannot occupy the same space at
the same time. But a wave spreads, as it travels, occupying a larger region of space.
A wave is specified by wavelength, frequency, amplitude, intensity, phase, and wave
velocity.
In the case of interference, diffraction, and polarization, light behaves as a wave
since the presence of two waves are required at the same time and at the same space
to explain these phenomena. But we know that two particles cannot occupy the same
position at the same time. Thus light behaves as a wave in these situations.
In the case of photoelectric effect, Compton Effect, emission and absorption of
radiation (blackbody radiation, for example) etc., the radiation behaves as a particle
(photon).
Thus we can conclude that radiation has dual nature (wave-like and particle-like).
But radiation cannot exhibit both the properties of a particle and a wave simultane-
ously.

3
 1.1. WAVE-PARTICLE DUALITY

1.1.1 de Broglie’s Hypothesis

We concluded that light (radiation) exhibits dual nature in the previous section. Due to
this result, in 1924, Louis de Broglie put forth a suggestion that matter also exhibits
dual nature, just like light, i.e., matter which is made up of discrete particles (for
example, atoms, protons, electrons etc.) might exhibit wave like properties under
appropriate conditions. These waves associated with moving material particles were
called matter waves.
Here we derive an expression for wavelength of such a wave by analogy. Consider
a particle of mass m moving with velcity v. From Einstein’s theory of relativity, we
have a relation between the particle’s mass and energy E given by

E = mc2 (1.1)

Now, we need an expression for energy in terms of a wave property like wavelength.
We have from Planck’s law, E = hν. Writing this in terms of wavelength (using
c = νλ), we get
hc
E= (1.2)
λ
Let’s equate (1.1) and (1.2), we get

hc
mc2 =
λ
h
λ=
mc
Since the particle is moving with velocity v, let’s replace c (the velocity of light) in
the above expression with v. So we have

h
λ=
mv
But we know that p = mv is the momentum of the particle. So finally, we have

h
λ= (1.3)
p

The wavelength λ of a matter wave associated with a particle moving with momen-
tum p is called the de Broglie wavelength.
Note: Look at the Planck’s formula for energy and de Broglie’s formula for wave-
length
h
E = hν and λ =
p
Both these formulae are indicating a relationship between particle characteristics (E
and p) and wave characteristics (ν and λ), and they are linked through the same
constant h.
The above formula for de Broglie wavelength was in terms of momentum or velocity
of the particle. We can also write the formula in terms of the particle’s kinetic energy

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 1.2. WAVE PACKETS

Ek = 12 mv 2 . We do it as follows:

1 1 2 2
Ek = mv 2 = mv
2 2m
p2
Ek =
2m
p
=⇒ p = 2mEk

Substitute this p in de Broglie’s formula

h
λ= √ (1.4)
2mEk

This is the formula for de Broglie wavelength in terms of the particle’s kinetic energy.
Now, consider a charged particle of charge q, mass m accelerated through a potential
difference (voltage) V . The work done on this particle due to the potential difference
is given by qV . This work done is converted into the particle’s kinetic energy, i.e.,
Ek = qV . Substitute this Ek in (1.4).

h
λ= √
2mqV

(Note: q is only magnitude of charge here.)

As a special case, consider the charged particle to be an electron. Then q = e,
where e = 1.6 × 10−19 C is the charge of the electron. Then the above formula becomes
 
h h 1
λ= √ = √ √
2meV 2me V
Here, h, m, e are all constants. After substituting in these constants and simplifying,
we get
12.27
λ = √ Å
V
where V is in volts and 1Å = 10−10 m.

1.2 Wave Packets

Let us now look at how to represent the de Broglie wave associated with any particle.
We will start by introducing a mathematical structure to the wave and later give a
physical meaning to it.

1.2.1 Phase Velocity

For a travelling undamped sinusoidal wave, the vertical displacement y of any point
on the wave can be written in terms of the point’s position x and time t as

y = A sin(ωt − kx) (1.5)

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 1.2. WAVE PACKETS

Figure 1.1: Travelling Wave

where A is the amplitude, ω is the angular frequency, and k is the wave number. ω
and k contain information about the wave’s frequency ν and wavelength λ through the
expressions ω = 2πν and k = 2π λ
.
Look at figure 1.1 for example. It shows the graph of a travelling wave with y on
the y-axis and x on the x-axis at an instant of time t with some given value of k and
ω. This graph can be thought of as the path traced by a vertically oscillating object
attached to a spring which also moves with a certain velocity v to the right. The dot
represents the vertical distance y of the oscillating object at x = 2 at this instant of
time.
In (1.5), the term (ωt − kx) gives the phase of the oscillating object. This term is
a constant with respect to time and thus we can write

d
(ωt − kx) = 0
dt
dx
ω−k =0
dt
dx ω
= (1.6)
dt k

If a point is imagined to be marked on a travelling wave, then it becomes a repre-

sentative point for a particular phase of the wave (for example, if the imagined point is
the top most location on the crest, then it represents the π/2 phase.), and the velocity
with which it is transported owing to the motion of the wave is called the phase veloc-
ity. Since in (1.6) x is the distance travelled, dx
dt
is taken as the phase velocity vphase .
Therefore we have
ω
vphase = (1.7)
k

Now, you might be tempted to conclude that this phase velocity represents the
velocity of the particle vparticle whose wave nature we are trying to understand. This is
not it as you will see soon.

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 1.2. WAVE PACKETS

Figure 1.2: Wave packet formed by superposition of two waves of differing wavelengths

1.2.2 Group Velocity

When a group of two or more travelling waves, differing slightly in wavelengths, are
superimposed on each other, a resultant pattern emerges in the shape of variation in
amplitude (see blue curve in figure 1.2). Such variation represents the wave group as
a whole, and is called the wave packet (represented by the red curve in the figure).
If the velocities of the component waves are equal, then the envelope enclosing the
amplitude variation pattern also, or the wave packet also, travels with the same velocity
as the common velocity of the waves. Since the group consists of waves of different
wavelengths, they are bound to move with different velocities in a dispersive medium,
at which time, the envelope or the wave packet is carried with a velocity which will
be different from the others (given the frequency of the constituent waves are also
different). The velocity with which the wave packet moves is called the group velocity.
Group velocity is the velocity with which the envelope enclosing a wave group (called
wave packet, formed due to superposition of two or more travelling waves of slightly dif-
ferent wavelengths) is transported. It is the velocity with which the energy transmission
occurs in a wave.
It may be noted that the phase velocity cannot be defined for a wave packet.
If we have two travelling waves with angular frequency ω and ω + ∆ω respectively
and wave number k and k + ∆k respectively, where the ∆ quantities are small, then it
can be shown that the velocity of the wave packet, called the group velocity, is
∆ω
vgroup =
∆k
In the limit, we have
∆ω dω
−→
∆k dk
Therefore we get the expression for group velocity as
dω
vgroup = (1.8)
dk
This expression is applicable in general to a superposition of more than two trav-
elling waves also.
It turns out that the group velocity (and not the phase velocity) is the velocity of
the particle whose wave nature we are trying to understand. To see why, let’s find the
relation between vgroup and vparticle .

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 1.2. WAVE PACKETS

Relation Between Group Velocity and Particle Velocity

Consider the expression for group velocity (1.8),
dω
vgroup =
dk
Here, ω(= 2πν) and k(= 2π λ
) are properties of the wave. We need to introduce
particle properties, energy E and momentum p, here. But we know the relations
connecting the two pictures:
E
E = hν −→ ν =
h
and
h
λ=
p
Therefore, we can write
E
ω = 2πν = 2π
h
and
1 p
k = 2π = 2π
λ h
Let us consider some small increments dω and dk in ω and k respectively. Then
we can write
dE
dω = 2π
h
and
dp
dk = 2π
h
Substitute these in (1.8). We have
dE
2π
vgroup = h
dp
2π
h
dE
vgroup = (1.9)
dp
So we have a relation between the group velocity and the properties of the particle.
Now, consider a particle of mass m moving with velocity vparticle in free space, i.e., no
external forces, which means the potential energy of the particle is zero. Therefore the
total energy E of the particle is completely due to its kinetic energy. So we can write
1 2 p2
E = mvparticle =
2 2m
where p = mvparticle is the momentum of the particle. Substitute this E in (1.9)
 2
d p
vgroup =
dp 2m
p
vgroup =
m

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 1.2. WAVE PACKETS

But p = mvparticle . Thus we have finally

vgroup = vparticle (1.10)

Therefore, we can conclude that the de Broglie wave group (made up of many
travelling waves) associated with a free particle travels with a velocity equal to the
velocity of the particle itself.

Correlation between de Broglie Wavelength, Heisenberg’s Uncertainty prin-

ciple, and wave packet
The key takeaway from the preceding section is that to represent a particle as a wave, a
single travelling wave is not enough. The wave nature of the particle can be represented
accurately only by taking a superposition of multiple travelling waves with varying
wavelengths. But by de Broglie’s formula (1.3), these varying wavelengths must come
from particles with different momenta. This means that we are considering multiple
versions of the same particle but with different momenta all together at once to describe
that one particle. So then, just like we said a wave packet is a superposition of multiple
travelling waves with different wavlengths, we can say that the particle we want to
describe is in a superposition of having all the different associated momenta at once.
This means there is an uncertainty regarding the particle’s momentum (which is it
among the many?).
Now, we said that the velocity with which the wave packet is moving is same as
the velocity of the particle which it is describing. But we know material particles are
point-like, whereas the wave packet as shown above occupies some finite space (which
would not be a good representation of the particle’s position). In other words, the wave
packet suggests an uncertainty in position of the particle. So if we could make the wave
packet occupy less space (i.e., make it localized and as a result reduce the uncertainty
in position), then it becomes a good approximation for a point-like particle. But it
can be shown that to make the wave packet smaller, we need to add more travelling
waves with even more different wavelengths to the wave superposition, which means the
particle superposition we mentioned earlier will have even more different momentum
values and the uncertainty of the momentum increases. So in other words, if we wish
to decrease the uncertainty in the particle’s position, the uncertainty in its momentum
increases.
Now let’s say we don’t care about making the wave packet localized, but want to
know the momentum with less uncertainty. This means we want the particle superpo-
sition to have only a few momentum values. But this will mean the wave superposition
will have only a few travelling waves with slightly differing wavelengths. It can be
shown that such a wave packet won’t be localized but spread out in space, which
means the uncertainty in position increases. So in other words, if we wish to decrease
the uncertainty in the particle’s momentum, the uncertainty in its position increases.
Notice here that I have avoided using the phrase ’zero uncertainty’. A value of zero
for the particle’s uncertainty in position and momentum has no physical significance as
will be explained now. Let’s say the uncertainty in momentum is zero. That is, there is
only one momentum value associated with the particle. This means the wave describing
this particle is a single travelling wave (and not a wave packet) which we know extends

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 1.3. HEISENBERG’S UNCERTAINTY PRINCIPLE

throughout space. In other words, the particle’s position can be anywhere in space
(technically, we say that the particle is in a superposition of being at all possible
positions), which means the uncertainty in position is infinite, which has no physical
significance. On the other hand, let’s say the uncertainty in position is zero. That is,
the wave packet describing the particle is localized to a single point (instead of having
a finite size). But to form such a wave packet, we need to add infinitely many travelling
waves with all possible wavelengths, which means the particle is in a superposition of
having all possible momentum values, which implies that the uncertainty in momentum
is infinte, which again has no physical significance.
We observe from the above discussions that there is an inverse relationship between
the uncertainties of position and momentum of a particle. The Heisenberg’s uncertainty
principle simply quantifies this relationship in the form of an inequality.

1.3 Heisenberg’s Uncertainty Principle

In classical mechanics, a particle occupies a definite place in space and possesses a def-
inite momentum. By knowing the position and momentum of a particle at any given
instant of time and knowing its interactions with its surroundings, it is possible to eval-
uate its position and momentum at any later stage, and the trajectory of the particle
could be continuously traced. But in quantum mechanics, there is an inherent inability
to accurately determine the position and momentum of a particle simultaneously.
According to the Heisenberg’s Uncertainty Principle, it is impossible to determine
simultaneously both the position and momentum of a particle with complete accuracy.
This is represented quantiatively by the following inequality:

h̄
∆x∆p ≥ (1.11)
2
where ∆x is the uncertainty in determining the position of the particle, ∆p is the
uncertainty in determining the momentum of the particle, and h̄ is called the reduced
Planck’s constant given by
h
h̄ =
2π
(Note that here we are considering motion in only one dimension. If the motion was
in three dimensions, we would have three inequalities relating the three coordinates
(x, y, z) with the three components of momentum (px , py , pz ) respectively.)
Two consequences of the Heisenberg’s uncertainty principle are as follows:

ˆ An increase in the accuracy of determination of a particle’s position means a

decrease in the value of its uncertainty ∆x. As per (1.11), a decrement in the
value of ∆x must simultaneously result in the increment in the value of ∆p since
the right hand side of the equation is a constant. So in such a case, there is a
decrease in the accuarcy of simultaneous determination of momentum.

ˆ ∆x and ∆p can never be zero in the microscopic realm. If one of these is zero,
then the left hand side of (1.11) becomes zero and the inequality won’t hold.
This tells us that our inability to accurately determine these quantities is not

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 1.3. HEISENBERG’S UNCERTAINTY PRINCIPLE

because of poor instruments or less sophisticated technology, but is due to the

inherent nature of the system under investigation. No matter how advanced
an instrument one invents, it can never determine these quantities with 100%
accuracy. (Remeber that this relation applies to only microscopic (quantum) par-
ticles. Classically, for macroscopic particles, h̄ is such a small quantity compared
to the other quantities involved that it may be assumed to be zero. So only in
this case, the uncertainties can become zero.)

1.3.1 Principle of Complementarity

The complementarity principle holds that objects have certain pairs of complementary
properties which cannot all be observed or measured accurately simultaneously. One
of these pairs is position and momentum. Other pairs include

h̄
ˆ Energy (E) and time (t) with ∆E∆t ≥
2
h̄
ˆ Angular displacement (θ) and angular momentum (L) with ∆θ∆L ≥
2
The reason these specific pairs satisfy this principle and not others is seen in the
formalism of quantum mechanics which is beyond the scope of this course. But the
key takeaway of this principle is the fact that setting up an experiment to measure one
quantity of a pair (say, position of an electron) excludes the possibility of accurately
measuring the other (momentum, in this case), yet understanding both experiments is
necessary to characterize the object under study. In other words, both the light and
particle nature of any object together can give us the complete picture of the object.

1.3.2 Application of Heisenberg’s Uncertainty Principle

Non-existence of electron in the nucleus of an atom (non-relativistic case)
In the β-decay process of radioactive radiation, it was observed that the emitted radia-
tion was composed of electrons (β rays), and the energy of these electrons was found to
be in the range of 3 to 4 M eV . But we know that electrons exist outside the nucleus of
an atom and not inside it. So does this experimental observation suggest that electrons
can also be found inside the nucleus? We’ll use Heisenberg’s Uncertainty Principle to
check whether this is true or not.
The typical radius of an atomic nucleus is nearly 5 × 10−15 m. If an electron is to
exist inside the nucleus, then the uncertainty in its position ∆x should not exceed this
value, i.e., we can take ∆x = 5 × 10−15 m. Then from (1.11) we get the uncertainty in
momentum ∆p as
h
∆p ≥
4π∆x
6.625 × 10−34
∆p ≥
4π × 5 × 10−15
∆p ≥ 1.05 × 10−20 Ns

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 1.4. WAVEFUNCTION

Now the momentum of the electron should have a minimum value equal to this
uncertainty, and we will assume that this is the case, i.e., p = 1.05 × 10−20 Ns.
Now, we know the relation between a particle’s kinetic energy and momentum is
given by
p2
Ek =
2m
Now, substituting the value of p from above and m = 9.1×10−31 kg (for an electron)
in this expression, we get
2
1.05 × 10−20
Ek =
2 × 9.1 × 10−31
Ek = 60.57 × 10−12 J
Ek ≈ 380MeV

We see that, theoretically, the electron must possess 380MeV of energy when it is
emitted from inside the nucleus. But experimentally we had only measured energy in
the range of 3 to 4 MeV. This shows that our assumption of considering electron to
exist inside the nucleus is wrong. So the electron does not exist in the nucleus.
(Note: It turns out that the electrons emitted in the β-decay process are due to
the decay of neutrons into protons, antineutrinos, and electrons. An electron as such
doesn’t exist in the nucleus on its own.)

1.4 Wavefunction
From the de Broglie’s hypothesis, we had associated a wave with a moving particle and
called it a matter wave, and the wavelength of this wave was given by the de Broglie’s
wavelength formula (1.3). This wave can be a function of position and time, just like
any other wave (waves on a string, electromagnetic waves, etc.). The mathematical
form of this function of the wave is called the wavefunction of the particle and is
denoted by Ψ(x, t) for the one-dimensional case.
So far we haven’t given any physical meaning to the wavefunction (as in, what
does the wavefunction actually represent?). We will give one now called the Born’s
interpretation of a wavefunction.
According to Born, the wavefunction (representing a matter wave) is a probability
wave (or probability amplitude). The modulus-square of this probability amplitude
|Ψ(x, t)|2 is called the probability density P (x, t) and it tells us about the probability
of finding the particle at a position x at time t per unit length. (For three dimensions,
we have |Ψ(⃗r, t)|2 which is the probability of finding the particle at a position ⃗r at time
t per unit volume, hence the name density.) We take the modulus-square instead of
a regular square here because the wavefunction could be a complex quantity. So the
probability density can also be written as

P (x, t) = |Ψ(x, t)|2 = Ψ∗ (x, t)Ψ(x, t)

where Ψ∗ (x, t) is the complex conjugate of Ψ(x, t).

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

The probability density here is the probability per unit length. To determine actual
probabilities, i.e., a number between 0 and 1, we will consider the term

P (x, t)dx = |Ψ(x, t)|2 dx

which gives the probability P (x, t)dx of finding the particle between positions x and
(x + dx) at time t. (For three dimensions, we have P (⃗r, t)dV = |Ψ(⃗r, t)|2 dV which is
the propbability P (⃗r, t)dV of finding the particle between volumes V and (V + dV ) at
time t.)
We know from probability theory that the sum of all the different probabilities
corresponding to all possibile events must be equal to 1. Similarly, if there are different
probabilties of finding the particle at different regions in space, then the sum of all these
probabilities must be equal to 1. This is nothing but asserting that the particle has to
exist somewhere in space. This condition is called the normalisation condition and is
written as
Z ∞
P (x, t)dx = 1
−∞
Z ∞
=⇒ |Ψ(x, t)|2 dx = 1
−∞

A wavefunction which satisfies this condition is called a normalised wavefunction.

1.4.1 Properties of a wavefunction

An acceptable wavefunction has the following properties:
ˆ The wavefunction must be finite everywhere; because if it is infinite at a particular
point, then it means that there is an infinitely larger probability of finding the
particle at that particular point which is a clear violation of the uncertainty
principle.

ˆ The wavefunction must be single valued; because if it has more than one value
at a particular point then it means there is more than one value of probability
of finding the particle at that particular point, which is not possible.

ˆ The wavefunction must be continuous everywhere and must have continuous

first-order derivative everywhere.
Along with these properties, a wavefunction is postulated to contain all the infor-
mation that can be known about the system.

1.5 Schrodinger’s Time-Independent Wave Equa-

tion
Schrodinger’s equation is the fundamental equation of quantum mechanics. It is the
wave equation describing the behaviour of the wavefunction of a system. Sound waves
and waves in strings are described by the equations of Newtonian mechanics. Light

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

waves are described by Maxwell’s equations. Similarly, matter waves (wavefunctions)

are described by Schrodinger’s equation.
The wave equation that Schrodinger originally proposed is called the Schrodinger’s
time-dependent wave equation. After making a few assumptions and substitutions to
this original equation, we get the Schrodinger’s time-independent wave equation. We
will only learn about the latter.
Any kind of wave can be described by something called a general wave equation
such as
∂ 2 u(x, t) 1 ∂ 2 u(x, t)
= (1.12)
∂x2 v 2 ∂t2
where u(x, t) is the mathematical function representing the wave (like waves on a string,
electromagnetic waves, etc.) and v is the velocity of the wave. (Note that here we are
only considering the one-dimensional case.)
Since (1.12) is an equation for a general wave, we can consider the wavefunction
Ψ(x, t) representing the matter wave to also be described by a similar equation, i.e.,

∂ 2 Ψ(x, t) 1 ∂ 2 Ψ(x, t)
= (1.13)
∂x2 v2 ∂t2
where, again, v is the velocity of the wave (here, matter wave).
Now we will consider a solution to this equation which is of the form

Ψ(x, t) = ψ(x)e−iωt (1.14)

where ω = 2πν is the angular frequency associated with

√ the wave, ν is the frequency
of the wave, and i is the imaginary number, i.e., i = −1. (Note the presence of both
forms of the psi symbol Ψ and ψ. The former is a function of x and t while the latter
is a function of only x.)
Substituting (1.14) into (1.13), we get

∂ 2 (ψ(x)e−iωt ) 1 ∂ 2 (ψ(x)e−iωt )
=
∂x2 v2 ∂t2
2 2
d ψ(x) ω
e−iωt 2
= − 2 e−iωt ψ(x)
dx v
d2 ψ(x) ω2
= − 2 ψ(x)
dx2 v
In the second line, we have changed the partial derivative to an ordinary derivative
since the argument (i.e., ψ(x)) now is only a function of x.
Now, we know that ω = 2πν and v = νλ, where λ is the wavelength of the
wave. (Here, λ is the de Broglie wavelength since we are considering matter waves.)
Substituting ω and v in the above equation, we get

d2 ψ(x) 4π 2 ν 2
= − ψ(x)
dx2 ν 2 λ2
d2 ψ(x) 4π 2
= − ψ(x)
dx2 λ2

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

Now, from de Broglie’s hypothesis, the de Broglie wavelength λ is related to the

momentum p of the particle through the relation (1.3). Substituting this relation in
the above equation, we get
d2 ψ(x) 4π 2 p2
= − ψ(x)
dx2 h2
Now, we know that the kinetic energy of the particle Ek in terms of its momentum
p is given by
p2
Ek =
2m
where m is the mass of the particle.
So we have p2 = 2mEk . Substituting this into the above equation, we get
d2 ψ(x) 8π 2 mEk
=− ψ(x)
dx2 h2
If E and V (x) are the total energy and the potential energy of the particle, respec-
tively, then we have the relation
E = Ek + V (x) =⇒ Ek = E − V (x)
Here E is a constant and V (x) is a function of position.
Substituting this Ek in the above equation, we get
d2 ψ(x) 8π 2 m(E − V (x))
= − ψ(x)
dx2 h2
Let us use the reduced Planck’s constant (h̄ = h/2π) here. We get
d2 ψ(x) 2m(E − V (x))
=− ψ(x)
dx 2
h̄2
After rearranging the terms, we get the following equation
h̄2 d2 ψ(x)
− + V (x)ψ(x) = Eψ(x) (1.15)
2m dx2
This is the Schrodinger’s time-independent wave equation. The wavefunction ψ(x)
which is independent of time is also called a stationary state. It is called so because
the probability density for this state does not change with time. Let’s see how. We
have the expression for probability density as
P (x, t) = |Ψ(x, t)|2
But while deriving the time-independent Schrodinger wave equation, we had as-
sumed
Ψ(x, t) = ψ(x)e−iωt
Let’s substitute this in the expression for probability density. We get
P (x, t) = |Ψ(x, t)|2
= Ψ∗ (x, t)Ψ(x, t)
= ψ ∗ (x)eiωt ψ(x)e−iωt
= ψ ∗ (x)ψ(x)
=⇒ P (x) = |ψ(x)|2

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In the last line, we have dropped t in P because now it is independent of time, i.e., we
see here that the probability density is now independent of time for a stationary state.
We can also write (1.15) in the following form

h̄2 d2
 
− + V (x) ψ(x) = Eψ(x)
2m dx2
Ĥψ(x) = Eψ(x) (1.16)

h̄2 d2
where Ĥ = − + V (x) is called the Hamiltonian operator.
2m dx2
Now, (1.16) is called an eigenvalue equation, just like the eigenvalue equations we
see in linear algebra such as AX = λX, where A is a given matrix, X is a column
matrix (or a vector) which is called the eigenvector of A, and λ is a scalar which is
called the the eigenvalue of A. Similarly, in (1.16) Ĥ is a given operator (analogous to
matrix A), ψ(x) is called the eigenfunction of Ĥ and E is called the eigenvalue of Ĥ.
In linear algebra, given an n×n matrix A, we can find the n eigenvalues λi and their
corresponding eigenvectors Xi of A using the charactersistic equation det(A − λI) = 0
(where I is an n×n identity matrix). Then the eigenvalue equation for each eigenvector
is AXi = λi Xi , where i = 1, 2, . . . n. First we get the various eigenvalues corresponding
to A, such as λ1 , λ2 , λ3 , . . . , λn . Then corresponding to each of these eigenvalues, we
get the respective eigenvectors such as X1 , X2 , X3 , . . . , Xn .
We can do a similar thing for (1.16). The method is a little different (because we
have an operator here instead of an n × n matrix) but the end result is the same,
i.e., given an operator Ĥ, we can find both the eigenvalues (E1 , E2 , E3 , . . .) and the
corresponding eigenfunctions (ψ1 (x), ψ2 (x), ψ3 (x), . . .) of Ĥ.
To solve (1.16), we will need information about the potential energy V (x) in the
corresponding system. So knowing the system’s mass m and potential energy, we can
solve the above eigenvalue equation. This requirement of a mass and potential energy
to solve an equation is similar to the requirement of mass and forces to solve Newton’s
second law of motion (ma = F ). So Schrodinger’s equation can be regarded as the
quantum mechanical counterpart to the classical Newton’s second law.
In the case of three dimensions, (1.15) takes the form

h̄2 2
− ∇ ψ(⃗r) + V (⃗r)ψ(⃗r) = Eψ(⃗r)
2m
where ∇2 is the three-dimensional counterpart of the second-order derivative operator
called the Laplacian operator and is given by
∂2 ∂2 ∂2
∇2 = + +
∂x2 ∂y 2 ∂z 2

Expectation Value
Let’s say we are rolling a pair of dice and noting the sum of the two numbers. These
readings can range from 2, 3, 4, upto 12. Using a simple procedure, we can count the
different possible ways of getting these different readings. For example, there is only
one way to get a 2 (1+1), whereas there are three ways to get a 4 (1+3, 2+2, 3+1).

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The total number of all possible combinations is 6 × 6 = 36. Then, we can say that
1/36 is the probability of getting a 2; 4/36 is the probability of getting a 4, and so on.
In general, let’s say P (a) is the probability of getting a, where a = 2, 3, 4, . . . 12. So
P (2) = 1/36, etc.
Now, the mean value ⟨a⟩ of all the readings is given by the expression

12
X
⟨a⟩ = aP (a)
a=2

Solving this explicitly, we find that the mean value is equal to 7. This means that
the reading 7, on average, is relatively more likely to come up when physically rolling
the dice. That is why the mean value in this context is also called the expectation
value. It is important to note that if the expectation value is a certain reading, then
it does not imply the other readings won’t come up. For example, in our case, even
though we got an expectation value of 7, it does not mean that we won’t get any other
number when physically rolling a dice.
The idea of expectation value in quantum mechanics is similar to the case as de-
scribed above. Instead of rolling a dice and taking a reading, we perform an experiment
and make a measurement. As the readings of a dice come up with different probabili-
ties, so do the measurement values of the experiment. For example, if we perform an
experiment to determine the position of a particle, the first measurement might yield
some value with some probability whereas the second measurement might yield some
other value with its corresponding probability. (Note that the different measurements
being made here are on different but similarly prepared states of the particle. We are
not making measurements on the same state one after the other.)
So if P (x, t) is the probability of the particle to be at position x at time t, then
we can find the expectation value ⟨x⟩(t) of x as a function of time using a similar
expression as that mentioned above, but with a minor change. The above expression
was for a discrete quantity (a = 2, 3, 4, . . .), whereas here we have a continous quantity
(for example, x = 10, 3.1, -22.678, 0.00001 or any real number). So we need to change
the summation symbol into an integral as follows
Z ∞
⟨x⟩(t) = xP (x, t)dx
−∞

But we know that probailities are given by the square-modulus of the particle’s
wavefunction. So we can finally write the expectation value of position as
Z ∞
⟨x⟩(t) = x|Ψ(x, t)|2 dx
−∞

If the wavefunction is a stationary state, then the expectation value is independent

of time. For example, if we consider position, its expectation value for a stationary
state is given by
Z ∞
⟨x⟩ = x|ψ(x)|2 dx
−∞

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1.5.1 Application of Schrodinger’s time-independent wave equa-

tion
Particle in an infintely deep potential well (Particle in a 1D box)
Consider a particle of mass m present in one-dimensional space. We assume the po-
tential energy present in this space to be as follows
(
0 when 0 ≤ x ≤ L
V (x) =
∞ when x < 0 and x > L

The plot of V (x) against x is as shown in figure 1.3.

Figure 1.3: Infinitely deep potential well of width L

Considering each region of the potential energy plot seperately, we will solve the
equation
h̄2 d2 ψ(x)
− + V (x)ψ(x) = Eψ(x) (1.17)
2m dx2
First, consider the region x < 0 and x > L. Here V = ∞. Substituting this V in
(1.17), we get
h̄2 d2 ψ(x)
− + ∞ψ(x) = Eψ(x)
2m dx2
This equation will hold only if we take ψ(x) = 0. (If we pick a non-zero value, then
the LHS will be infinite whereas the RHS will be finite since E is a constant.)
So we have ψ(x) = 0 in the region x < 0 and x > L. This implies that there is zero
probability of finding the particle in this region, which makes sense because no particle
can exist in an infinte potential region (if it did, the energy of the particle would be
infinite, which is impossible).

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Now consider the region 0 ≤ x ≤ L. Here V = 0. Substituting this value of V in

(1.17), we get

h̄2 d2 ψ(x)
− = Eψ(x)
2m dx2
d2 ψ(x) 2mE
2
= − 2 ψ(x)
dx h̄
d2 ψ(x)
= −k 2 ψ(x)
dx2
where
2mE
k2 = (1.18)
h̄2
So we have the following differential equation

d2 ψ(x)
2
+ k 2 ψ(x) = 0
dx
The solution to this differential equation is of the form

ψ(x) = A sin(kx) + B cos(kx) (1.19)

where A and B are arbitrary constants which have to be determined. Remember that
we need to also determine k since it contains E, which is one of the things we’re trying
to find (eigenvalue of the eigenvalue equation (1.17)). We’ll find A, B, and k using the
boundary conditions and the wavefunction normalisation condition.
So what are the boundary conditions? To figure this out, we’ll have to use the
property of the wavefunction which states the wavefunction has to be continuous ev-
erywhere. Since we already know that ψ(x) = 0 outside of the region we are considering
now, ψ(x) will have to be zero even at x = 0 and x = L for it to be continuous. (If
it is not zero at these two points, then there will be a discontinuity between the two
regions which is not acceptable for a wavefunction.) So our boundary conditions are
ψ(0) = 0 and ψ(L) = 0.
Using the first boundary condition, we have

ψ(0) = A sin(0) + B cos(0)

0=0+B
=⇒ B = 0

So (1.19) now becomes

ψ(x) = A sin(kx) (1.20)
Using the second boundary condition, we have

ψ(L) = A sin(kL)
0 = Asin(kL)
=⇒ A = 0 or sin(kL) = 0

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

If A = 0, then from (1.20), we get ψ(x) = 0, which means the particle has zero
probability of being in this region (0 ≤ x ≤ L), which of course is not the case. So
A ̸= 0, which implies

sin(kL) = 0
=⇒ kL = nπ
nπ
k=
L
where n = 1, 2, 3, . . . is any positive integer. (Mathematically, n = 0 is also valid, but
we don’t consider it because it will give ψ(x) = 0.)
Since the value of k depends on n, we should write it as kn ,
nπ
kn = (1.21)
L
As we have determined k (now called kn ), we can determine the eigenvalue E (now
called En ). Substituting (1.21) in (1.18) (after changing k to kn ), we get

n2 π 2 2mEn
=
L2 h̄2
n2 π 2 h̄2 n2 h2
=⇒ En = or (1.22)
2mL2 8mL2
These En (E1 , E2 , E3 , . . .) are called the allowed energy eigenvalues (energy levels)
for the given system. And we see that these energy levels are quantised.
Setting n = 1 in (1.22) gives E1 , which is called the ground state (or zero-point)
energy level
π 2 h̄2
E1 =
2mL2
We can also write all other energy levels in terms of E1 as follows

En = n2 E1

So E2 = 4E1 , E3 = 9E1 , E4 = 16E1 , etc.

Also note that the lowest energy (i.e., E1 ) in this system is not zero. This is due
to the Heisenberg’s uncertainity principle. It is a general result in quantum mechanics
that the lowest energy of any kind of system is non-zero. This lowest energy is also
called the zero-point energy. (If E is zero, then it means that ∆E is also zero, which
is prohibited by the uncertainty principle.)
The seperation between consecutive energy levels increases as n increases and is as
shown in figure 1.4.
Now, remember that we still need to find A. (1.20) becomes
 nπx 
ψn (x) = A sin
L
(We changed ψ(x) to ψn (x) since it depends on n.)
We say that ψ1 (x), ψ2 (x), ψ3 (x), . . . are the energy eigenfunctions corresponding to
the energy eigenvalues E1 , E2 , E3 , . . . respectively.

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

Figure 1.4: Energy levels of a 1D box

The complete solution to this problem can be written as


0 when x < 0

  nπx 
ψn (x) = A sin when 0 ≤ x ≤ L (1.23)

 L
0 when x > L

To find A, we will use the normalisation condition

Z ∞
|Ψ(x, t)|2 dx = 1
−∞

But since we are using stationary states, the normalisation condition reduces to
Z ∞
|ψ(x)|2 dx = 1
−∞

Now, note that we have to split the integral into three parts corresponding to the
three regions in our solution (1.23), i.e.,
Z ∞ Z 0 Z L Z ∞
2 2 2
|ψn (x)| dx = |ψn (x)| dx + |ψn (x)| dx + |ψn (x)|2 dx
−∞ −∞ 0 L

Now, the first and the third integral on the RHS vanish because ψn (x) = 0 in those
regions. Therefore we are left with the following normalisation condition
Z L
|ψn (x)|2 dx = 1
0

Substituting ψn (x) here from (1.23), we get

Z L  nπx 
|A|2 sin2 dx = 1
0 L

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Here, we use the trigonometric identity

1 − cos 2θ
sin2 θ =
2

L
|A|2
Z   
2nπx
1 − cos dx = 1
2 0 L
  L
2nπx

sin
|A|2 
x − L 
 =1
2  2nπ 
L 0
2
 
|A| L
L− sin(2nπ) − 0 + 0 = 1
2 2nπ
L 2
|A| = 1
2 r
2
A=
L
where we have used the fact that sin(2nπ) = 0 for any integer n.
So the complete solution to our eigenvalue equation (1.16) is
n2 π 2 h̄2
En = (1.24)
2mL2


 0 when x < 0
r
ψn (x) = 2  nπx 
(1.25)
sin when 0 ≤ x ≤ L


 L L
0 when x > L
r
2  nπx 
The wavefunction ψn (x) = sin is called the normalised wavefunction.
L L
The eigenfuction
r corresponding to n = 1 is called the ground state and is given by
2  πx 
ψ1 (x) = sin . The eigenfunction corresponding to n = 2 is called the first
L L r  
2 2πx
excited state and is given by ψ2 (x) = sin . Similarly we have the second,
L L
third, fourth etc., excited states for n = 3, 4, 5, etc., respectively.
In summary, each energy eigenvalue corresponds to one energy eigenfunction
r
π 2 h̄2 2  πx 
E1 = =⇒ ψ1 (x) = sin
2mL2 L L
r
2 2
 
4π h̄ 2 2πx
E2 = =⇒ ψ2 (x) = sin
2mL2 L L
2
r
9π 2 h̄
 
2 3πx
E3 = =⇒ ψ3 (x) = sin
2mL2 L L
..
.

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 1.5. SCHRODINGER’S TIME-INDEPENDENT WAVE EQUATION

Figure 1.5: ψn (x) vs. x Figure 1.6: |ψn (x)|2 vs. x

The plots of ψn (x) vs x and |ψn (x)|2 vs x for n = 1, 2, 3, 4 are shown in figure 1.5
and figure 1.6 respectively.
From figure 1.6, we see that for n = 1, there is higher propbability for the particle
to be present near the center of the box than at the ends. But for n = 2, there is lower
probability for the particle to be near the center (it is infact zero exactly at the center)
whereas the probability is higher near x = L/4 and x = 3L/4. Similar observations
can be made for n = 3, 4 states.

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