Course: Engineering Physics

Course Code: 21PH1C01

Semester: I Sem D Section
Branch: Computer Science and Engineering
Course Instructor: Dr. Sankarshan B. M.
 Quantum Mechanics

Dr. Sankarshan B. M.
Assistant Professor
Department of Physics
The National Institute of Engineering
Mandavadi Road, Mysuru - 570 008
 Time independent Schrödinger wave equation

The wave function describing the de Broglie wave can be

Time
written in complex notation as
independent
Schrödinger
wave Ψ = Ae i(kx−ωt) (1)
equation

Eigenfunctions
and where, Psi is the total wave function, A is a constant and ω is
Eigenvalues

Eigenfunctions: the angular frequency of the wave.

Operator
Operator
Dierentiating equation (1) w.r.t. x twice we get
mechanism in
Quantum
Mechanics
dΨ
Eigenvalues:
= (ik)Ae i(kx−ωt)
Applications dx
of
Schrödinger
wave
equation d 2Ψ
innite potential = (ik)(ik)Ae i(kx−ωt) = −k 2 Ψ
well dx 2
Normalization:
particle in an
innite potential
well
 Substituting
Time
2π
independent
Schrödinger
k=
wave
λ
equation
we get
d 2Ψ 2
 
4π
Eigenfunctions
and
=− Ψ (2)
Eigenvalues

Eigenfunctions:
dx 2 λ2
Operator
Operator
mechanism in
For a particle of mass m moving with velocity v, Total energy
Quantum
Mechanics
Eigenvalues: p2
Applications
E = KE + PE = +V
of
2m
Schrödinger
wave
m2 v 2
equation [∵ KE = 12 mv 2 = 2m
]
innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
equation h2
E= +V
Eigenfunctions 2mλ2
and
Eigenvalues h h
Eigenfunctions:
[∵ λ= p =⇒ p = λ]
Operator
Rearranging,
Operator
mechanism in
Quantum 1 2m(E − V)
Mechanics
2
= 2
(3)
Eigenvalues: λ h
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 1
Time
Substituting in equation (2),
independent λ2
Schrödinger
wave
d 2Ψ 2
 
equation 8π m
=− (E − V )Ψ
Eigenfunctions
and
dx 2 h2
Eigenvalues

Eigenfunctions: or
Operator
d 2Ψ 2
 
Operator 8π m
mechanism in
Quantum
+ (E − V )Ψ = 0 (4)
Mechanics dx 2 h2
Eigenvalues:

Applications Equation (4) is called Time independent Schrödinger wave

of
Schrödinger equation in one dimension.
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Eigenfunctions:

We can dened eigenfunctions as follows

Time
independent Eigenfunctions are those wave functions of quantum
Schrödinger
wave mechanics which possess the properties that they are single
equation
valued and nite everywhere, and also their rst derivatives
Eigenfunctions
and with respect to their variables are continuous everywhere.
Eigenvalues

Eigenfunctions: Quantum mechanics gives rules for extracting information

Operator
Operator
mechanism in
from Ψ to predict the results of measurements (as allowed
Quantum
Mechanics by Heisenberg's uncertainty principle).
Eigenvalues:
The rule consists of certain mathematical operations which
Applications
of
Schrödinger
are to be performed on Ψ in designated ways.
wave
equation The specic type of operation need to be performed is
innite potential
well identied through what is known as operator.
Normalization:
particle in an
innite potential
well
Time An operator is a symbol or a code which directs one to perform
independent
Schrödinger an operation on the function which follows the symbol.
wave
equation Examples are given in the table below.
Eigenfunctions
and
Eigenvalues

Eigenfunctions: Example
√ Operator Operation
Operator √
Operator 3 Take the square root
mechanism in
Quantum
Mechanics 25 ×6 × Multiply the two quantities on either of
Eigenvalues: d 3 d
Applications
dxR(x + 3) dx Take the rst derivative with respect
x 2 dx
R
of ()dx Integrate with respect to x
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Operator mechanism in Quantum Mechanics

Time
independent
Schrödinger
wave Related to each type of measurement there is one kind of
equation
operator.
Eigenfunctions
and For example, to obtain the momentum values, there is
Eigenvalues

Eigenfunctions: momentum operator, and to obtain energy values there is

Operator
Operator energy operator etc.
mechanism in
Quantum
Mechanics The table of operators for a few physical observables are
Eigenvalues:
listed in the table of operators.
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
equation
Table: Table of Operators
Eigenfunctions
and
Physical observable Operator Operator symbol
Eigenvalues h ∂
Eigenfunctions: Momentum
2πi ∂x
P̂
2
Operator ∂2
Operator Kinetic energy − 8πh2 m ∂x 2 T̂
mechanism in 2
∂2
Quantum
Mechanics Total energy − 8πh2 m ∂x 2 + U Ĥ
Eigenvalues:
Position x X̂
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Eigenvalues:

Time
independent
Schrödinger
wave
equation
Once the eigenfunctions are known, quantum mechanical

Eigenfunctions operators could be used to evaluate the physical

and
Eigenvalues observables such as energy in which case each of the
Eigenfunctions:
Operator
eigenfunctions provide one energy value.
Operator
mechanism in Since there is only a restricted set of eigenfunctions, there
Quantum
Mechanics
Eigenvalues: is also restricted set of energy values.

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 But all eigenfunctions when operated by the operators may
not give proper result or value for that physical observable.
Time
independent Because, it is also postulated in Quantum Mechanics that
Schrödinger
wave
the only possible values that can be observed of a physical
equation
quantity like angular momentum, energy etc., of a system
Eigenfunctions
and are the values λ in the operator equation
Eigenvalues

Eigenfunctions:
Operator ÂΨ = λΨ
Operator
mechanism in
Quantum
Mechanics
Eigenvalues:
where  is the operator for the physical quantity and
Applications
of Ψ is eigenfunction
Schrödinger
d d2
wave for e.g. dx e ax = ae ax , dx 2 (sin 2x) = −4(sin 2x) etc.,
equation

innite potential
i.e., the eigenfunction should be such that, the operator
well
Normalization:
operating on it produces back the wavefunction multiplied
particle in an
innite potential
by a constant (here it is λ).
well
Time
independent
Schrödinger
wave
Such values obtained for a physical observable are called
eigenvalues.
equation

Eigenfunctions
and
Eigenvalues If it is energy operator operating on Ψ, then they are called
Eigenfunctions:
Operator
energy eigenvalues
Operator
mechanism in
Quantum
If it is momentum operator that operates on Ψ, then they
Mechanics
Eigenvalues: are called momentum eigenvalues... so on.

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Energy eigenvalues of a Particle in one-dimensional,
innite potential well (Potential well of innite
depth):

Time
independent Suppose a particle of mass m is free to move in the
Schrödinger
wave x -direction only in the region from x =0 to x = a. In this
equation
region its potential V will be zero.
Eigenfunctions
and
Outside this region, it is taken to be innite, (which means
Eigenvalues

Eigenfunctions:
Operator
that the particle is bound within the limits x =0 to x = a).
Operator
mechanism in Such a conguration of potential in space is called innite
Quantum
Mechanics
Eigenvalues:
potential well.
Applications A particle bound within such an innite potential dened
of
Schrödinger in 3-dimensions is referred to as particle in a box.
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
equation
Outside the well, the Schrödinger equation is,
Eigenfunctions
and
Eigenvalues d 2 ψ 8π 2 m
Eigenfunctions: + (E − ∞)ψ = 0 ( since V = ∞) (5)
Operator dx 2 h2
Operator
mechanism in
Quantum
Mechanics
Eigenvalues:

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time This equation holds good only if ψ = 0.
independent
Schrödinger The only possible solution for the above equation is that
wave
equation ψ=0 at the wall and also everywhere outside the well.
Eigenfunctions
and
..... condition I
Eigenvalues

Eigenfunctions:
Since ψ=0 also means |ψ|2 = 0, the particle cannot be
Operator
found at all outside the well.
Operator
mechanism in
Quantum Inside the well, the Schrödinger's equation is given by
Mechanics
Eigenvalues:

Applications d 2 ψ 8π 2 m
of + Eψ = 0 ( Since V = 0) (6)
Schrödinger
wave
dx 2 h2
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 or
h2 d 2ψ
 
Time − 2 = Eψ (7)
independent
Schrödinger
8π m dx 2
wave
equation This is of the form Ĥψ = E ψ
Eigenfunctions
As per the postulate of Quantum Mechanics, this should be an
and
Eigenvalues eigenvalue equation,
Eigenfunctions:
Operator In Eq. (6), putting
Operator
mechanism in
Quantum 2
Mechanics 8π m
Eigenvalues:
2
E = K2 (8)
Applications
h
of
Schrödinger We have,
wave
d 2ψ
equation
+ K 2ψ = 0
innite potential
well dx 2
Normalization:
particle in an
innite potential
well
 Discussion of the solutions:

Time
independent The solution for th above equation is given by,
Schrödinger
wave
equation
ψ = C cos Kx + D sin Kx (9)
Eigenfunctions
and
Eigenvalues But ψ=0 at x = 0, as per condition I.
Eigenfunctions:
Operator ∴ Eq (9) becomes,
Operator
mechanism in
Quantum
Mechanics 0 = C cos 0 + D sin 0
Eigenvalues:

Applications
of ∴C =0 (10)
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Again as per condition I, ψ=0 at x = a, for which Eq (9)
becomes
Time
independent
0 = C cos Ka + D sin Ka
Schrödinger
wave
equation
From Eq (10) we have C = 0. Hence the above equation
becomes,
Eigenfunctions
and
Eigenvalues
D sin Ka = 0
Eigenfunctions:
Operator Here, D need not be = 0.
Operator
mechanism in
Quantum
Mechanics ∴ sin Ka = 0
Eigenvalues:

Applications
of or
Schrödinger
wave Ka = nπ
equation

innite potential
well where n = 0, 1, 2, 3, . . . . . . n is called quantum number which is
Normalization:
particle in an either zero or a positive integer.
innite potential
well
Time
independent
nπ
Schrödinger
wave
∴K = (11)
equation
a
Eigenfunctions Substituting for C and K from Eqs (10) and (11), Eq (9) can
and
Eigenvalues now be written as,
Eigenfunctions: nπ
Operator ψn = D sin x (12)
Operator a
mechanism in
Quantum
Mechanics From Eq (8),
Eigenvalues:
K 2 h2
Applications E=
of 8π 2 m
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Using Eq (11), the above equation becomes,

Time
independent
n2 h2
E= (13)
8ma2
Schrödinger
wave
equation

Eigenfunctions As already mentioned, n can have only integer values

and
Eigenvalues 0, 1, 2, 3, . . . . . .
Eigenfunctions:
Operator
Operator
The corresponding values that E takes are the energy
mechanism in
Quantum eigenvalues.
Mechanics
Eigenvalues: The lowest permitted state of energy is referred to as the
Applications
of
ground state energy.
Schrödinger
wave Thus zero point energy is taken as the ground state energy.
equation

innite potential The energy states, corresponding to n>1 are called

well
Normalization: excited states.
particle in an
innite potential
well
 In Eq (13), the value zero for n is not acceptable because,
Time
independent
when n = 0, ψn = 0
Schrödinger
wave
by Eq (12), which means to say that the electron is not
equation
present inside the box which is not true. Hence the lowest
Eigenfunctions
and acceptable value for n is 1.
Eigenvalues

Eigenfunctions: Consequently the lowest allowed energy corresponds to

Operator
Operator n=1 which is called the zero point energy.
mechanism in
Quantum
Mechanics The zero point energy of an electron in an innite potential
Eigenvalues:
well is given by,
Applications
of h2
Schrödinger Ezero-point =
wave 8ma2
equation

innite potential
well
which represent the permitted solution.
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
The lowest permitted stat of energy is referred to as the
wave
equation
ground state energy.
Eigenfunctions
and Thus zero point energy is taken as the ground state energy.
Eigenvalues

Eigenfunctions: The energy states corresponding to n>1 are called

Operator
Operator
mechanism in
excited states.
Quantum
Mechanics
Eigenvalues:
To evaluate D in Eq (12) one has to perform the
normalization of the wavefunction.
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Normalization:

The integral of the square of the wave function over the entire
space in the well must be equal to unity because, there is only
Time one particle and at any time it is present somewhere inside the
independent
Schrödinger well only. Therefore,
wave
equation Z a
Eigenfunctions |ψ|2 ds = 1 (14)
and
Eigenvalues
0
Eigenfunctions:
Operator
Operator
Substituting for ψn from Eq (12), we have,
mechanism in
Quantum
Mechanics
Z a
nπ
Eigenvalues: D 2 sin2 xdx = 1
Applications 0 a
of
Schrödinger
wave But, we know that,
equation

innite potential
well 1
Normalization: sin2 θ = (1 − cos 2θ)
particle in an 2
innite potential
well
Time
independent
Schrödinger
 Z a Z a 
wave 2
1 1 2nπ
equation ∴D dx − xdx = 1 cos
2 0 a2 0
Eigenfunctions
and a
D2
 
Eigenvalues a 2nπx
Eigenfunctions: x− sin =1
Operator 2 2nπ a 0
Operator
mechanism in
Quantum or
Mechanics
Eigenvalues:
D2 h a i
a− sin(2nπ) = 1
Applications a 2nπ
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
or
independent D 2a
Schrödinger =1 [ since sin(2nπ) = 0]
wave 2
equation
r
Eigenfunctions 2
and D=
Eigenvalues a
Eigenfunctions:
Operator Thus the normalized wavefunction of a particle in a
Operator
mechanism in
Quantum one-dimensional innite potential well is given by
Mechanics
Eigenvalues: r
2
 nπ 
Applications
of ψn = sin x (15)
Schrödinger a a
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Eigenfunctions, Probability densities and energy
eigenvalues for particle in an innite potential well:

Time
independent Since the particle in an innite well is a problem under
Schrödinger
wave
quantum mechanical conditions, the prime questions to be
equation
considered are, the most probable location of the particle
Eigenfunctions
and in the well and its energies, both to be evaluated for the
Eigenvalues

Eigenfunctions:
dierent permitted states.
Operator
Operator Let us analyse the same here.
mechanism in
Quantum
Mechanics Following Eq (12), we can write the eigenfunctions
Eigenvalues:

Applications
ψ1 , ψ2 , ψ3 , . . . . . . for particle in the well by putting
of n = 1, 2, 3, . . . . . . respectively in the equation.
Schrödinger
wave Let us consider the rst 3 cases.
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Case (i), n=1

Time
independent
Schrödinger
This is the ground state and the particle is normally found in
wave
equation
this state.

Eigenfunctions
and
Eigenvalues

Eigenfunctions:
Operator
Operator
mechanism in
Quantum
Mechanics
Eigenvalues:

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave For n = 1, the eigenfunction is,
equation
π 
Eigenfunctions
and ψ1 = D sin x, from Eq (12)
Eigenvalues a
Eigenfunctions:
Operator
Operator
In the above equation ψ1 = 0 for bothx =0 and x = a.
mechanism in
Quantum
Mechanics
But ψ1 has maximum value for x = (a/2).
Eigenvalues: Thus a plot of ψ1 versus x will be as shown in gure.
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
equation A plot of |ψ1 |2 is 0 both at x =0 and at x = a.
Eigenfunctions
and
It is maximum at x = (a/2).
Eigenvalues

Eigenfunctions: It means to say that, in ground state the particle cannot be

Operator
Operator found at all at the walls of the well, and the probability of
mechanism in
Quantum
Mechanics
nding it is maximum at the central region.
Eigenvalues:

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
Regarding the energy of the particle, using Eq (13), the
independent
Schrödinger
energy in the ground state (which is the same as the zero
wave
equation
point energy E0 ) is got by putting n = 1.
Eigenfunctions
and
Eigenvalues h2
Eigenfunctions: E1 = = E0 (16)
Operator 8ma2
Operator
mechanism in
Quantum
Mechanics
This is the energy eigenvalue for the ground state.
Eigenvalues:
Further, if E0 is the energy in the nth excited state, then
Applications
of from Eqs (13) and (16),
Schrödinger
wave
equation

innite potential
E n = n 2 E0 (17)
well
Normalization:
particle in an
innite potential
well
 Case(ii), n = 2:

Time
independent
Schrödinger
wave
equation

Eigenfunctions
and
Eigenvalues

Eigenfunctions:
Operator
Operator
mechanism in
Quantum
Mechanics
Eigenvalues:

Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 This is the rst excited state i.e., the next immediate higher
state permitted for the particle after the ground state.
Time
independent The eigenfunction for this state is,
Schrödinger
wave  
equation 2π
ψ2 = D sin x
Eigenfunctions
and
a
Eigenvalues

Eigenfunctions:
Operator
Now, ψ2 = 0 for the values x = 0, a/2 and a. Also, ψ2
a 3a
Operator
mechanism in
reaches maximum for x= 4
and
4
.
Quantum
Mechanics
Eigenvalues:
These facts are seen in the plot of ψ2 versus x shown in

Applications
gure.
of
Schrödinger The plot of |ψ2 |2 versus x is shown in gure. It is seen
wave
equation that |ψ2 |2 = 0 at x = 0, a/2 and a.
innite potential
well
Normalization:
It means that in the rst excited state the particle cannot
particle in an
innite potential be observed either at the walls, or at the center.
well
Time
independent
Further, from (17), for n=2
Schrödinger
wave
h2
 
equation
E2 = 4
Eigenfunctions 8ma2
and
Eigenvalues

Eigenfunctions: This is the energy eigenvalue for the rst excited state. Also,
Operator
Operator
mechanism in
Quantum
Mechanics
E 2 = 4 E0
Eigenvalues:

Applications Thus the energy in the rst excited state is 4 times the zero
of
Schrödinger point energy.
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 Case (iii), n = 3:

Time
independent
Schrödinger
wave
equation

Eigenfunctions
and
Eigenvalues

Eigenfunctions:
Operator
Operator
mechanism in
Quantum
Mechanics
Eigenvalues:

Applications This is the second excited state.

of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Following the same analysis as carried out earlier, we have
Schrödinger
wave
the eigenfunction for the second excited state as,
equation

Eigenfunctions  
and
3π
Eigenvalues
ψ3 = D sin x
Eigenfunctions:
Operator
a
Operator
mechanism in
Quantum
ψ3 = 0 for x = 0, a/3, 2a/3 and a.
Mechanics
Eigenvalues: ψ3 will have maximum value for x = a/6, a/2 and 5a/6.
Applications
of
These facts are revealed in the plot ψ3 versus x.
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
 The plot of |ψ3 |2 versus x is shown in gure has maxima
Time
independent at x = a/6, a/2 and 5a/6 which also imply the locations at
Schrödinger
wave which the particle is most likely to be found.
equation

This case corresponds to the second excited state. As in

Eigenfunctions
and
the earlier cases, using Eq (17), the energy in this state is
Eigenvalues

Eigenfunctions: given by,

Operator
h2
 
Operator
mechanism in
Quantum
E3 = 9
Mechanics 8ma2
Eigenvalues:

Applications
This is the energy eigenvalue in the second excited state.
of
Schrödinger Thus,
wave
equation E3 = 9 E0
innite potential
well
Normalization:
particle in an
innite potential
well
 Energy eigenvalues for a free particle:

Free particle means, it is not under the inuence of any kind of

Time
independent eld or force. Thus it has zero potential i.e., V = 0. Hence
Schrödinger
wave Schrödinger's equation becomes,
equation

Eigenfunctions
d 2 ψ 8π 2 m
and
+ Eψ = 0
Eigenvalues

Eigenfunctions:
dx 2 h2
Operator
Operator or
h2 d 2ψ
mechanism in
 
Quantum
Mechanics − 2 = Eψ
Eigenvalues: 8π m dx 2
Applications
of The above equation holds good for a particle for a particle for
Schrödinger
wave which the potential V =0 over the entire space (no boundaries
equation

innite potential at all).

well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
We know that in the case of particle in an innite potential
equation
well, the condition V =0 holds good only over a nite
Eigenfunctions
and width `a' and outside this region, V = ∞.
Eigenvalues

Eigenfunctions: Since for a free particle, V =0 holds good everywhere, we

Operator
Operator can extend the case fo particle in an innite potential well
mechanism in
Quantum to the free particle's case, by treating the width of the well
Mechanics
Eigenvalues:
to be innity, i.e., by allowing a = ∞.
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time We have the equation for energy for energy eigenvalues for a
independent
Schrödinger particle in an innite potential well as,
wave
equation

n2 h2
Eigenfunctions
E=
8ma2
and
Eigenvalues

Eigenfunctions:
Operator where n = 1, 2, 3, . . . . . .
Operator
mechanism in
Quantum Rearranging this equation, we have,
Mechanics
Eigenvalues:
2a √
Applications
n= 2Em
of
Schrödinger
h
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent Here, we see that, for a particle with constant energy E
Schrödinger
wave but conned in the well, n depends solely on `a'.
equation

Eigenfunctions
Hence, as a → ∞, n → ∞.
and
Eigenvalues In the limiting case when a = ∞, the particle is no more
Eigenfunctions:
Operator
conned in ay sort of well but free, at which time it also
Operator
mechanism in follows that, n = ∞, which essentially means that a free
Quantum
Mechanics particle can have any energy
Eigenvalues:

Applications i.e., the energy eigenvalues or the possible values of energy

of
Schrödinger are innite in number.
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well
Time
independent
Schrödinger
wave
Keeping in mind the energy level representation, we say
equation
that the permitted energy values are continuous.
Eigenfunctions
and All these mean, there is no discreteness in the allowed
Eigenvalues

Eigenfunctions: energy values. In other words, there is not quantization of

Operator
Operator energy in the case of a free particle and the problem is
mechanism in
Quantum dealt in classical mechanics.
Mechanics
Eigenvalues:
Thus a free particle is a `classical entity'.
Applications
of
Schrödinger
wave
equation

innite potential
well
Normalization:
particle in an
innite potential
well