BPHYEE202 Applied Physics for EEE Stream

Module II - Quantum Mechanics

Syllabus

Properties and Physical significance(including Probability density and Nor-

malization of wavefunction), Setting up of one dimensional time independent
Schrödinger wave equation. Application of Schrödinger wave equation: Energy
Eigen values and Eigenfunctions of a particle in a potential well of infinite
depth and extension to free particle, numerical problems.

The differential equation whose solution gives us the wave behavior of particles
is called the Schrödinger equation.The equation cannot be derived from any previ-
ous laws or postulates; like Newton’s equations of motion or Maxwell’s equations
of electromagnetism, it is a new and independent result whose correctness can be
determined only by comparing its predictions with experimental results. For non-
relativistic motion, the Schrödinger equation gives results that correctly account for
observations at the atomic and subatomic level.

Time Independent Schrödinger’s wave equation

Consider wave equation involving function ψ with respect to time and position. For
one dimensional wave
ψ(x, t) = ψo e−i(ωt−kx) (1)
We know that, angular frequency
2πE E
ω = 2πν = = (2)
h h̄
and wave vector
2π 2πp p
k= = = (3)
λ h h̄
Substitute equation (2) and (3) in (1)

ψ(x, t) = ψo e−i(Et/h̄−px/h̄) (4)

Differentiating the above equation wrt x, we get
   
dψ ip ip
= ψo e −i(Et/h̄−px/h̄)
= ψ
dx h̄ h̄

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Applied Physics for EEE Stream BPHYEE202

d2 ψ
 2
p
=− ψ (5)
dx 2
h̄2
Total energy is sum of kinetic energy and potential energy,
p2
E= +V
2m
p2 = 2m(E − V ) (6)
Substituting the above equation (6) in (5), we get

d2 ψ 2m(E − V )
+ ψ=0 (7)
dx2 h̄2
This equation is the steady state form of schrödinger’s equation. Because the
potential does not vary with time and total energy is constant. This describes the
wave behaviour of non relativistic particle.

Physical significance and Properties of wavefunc-

tion ψ
The quantity whose variations make up matter waves is called wave function ψ. The
value of the wave function associated with a moving body at a particular point x,
y, z in space at the time ‘t’ is related to the likelihood of finding the body there at
the time. Though ψ is complex quantity, |ψ|2 is always real. It gives the probability
of finding the particle in unit volume. It is called probability density(P). Larger the
value of |ψ|2 , larger will be probability. If dV is the volume element, then probability
of finding the particle within the volume dV is given by |ψ|2 dV .
If the probability of finding the particle in space is
Z ∞
P = |ψ|2 dV = 0
−∞

then particle does not exist.

If Z ∞
P = |ψ|2 dV = 1
−∞
then the particle is present. The above equation is known as Normalized Wave
Function. The properties of wave function ψ is it must be finite, single valued and
its derivatives must be continuous every where.

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Particle in one-dimensional box

V= V=

V=0

x=0 x=a

Consider a particle of mass m in one-dimensional box of length ‘a’, moving along

x-axis. The general schrödinger’s wave equation is given by
d2 ψ 2m(E − V )ψ
+ =0 (8)
dx2 h̄2
It is assumed that particle oscillates between walls. The collision with the walls is
perfectly elastic. Let
• V = 0 for 0 < x < a

• V = ∞ for x ≤ 0 and x ≥ a
The potential represents square well potential.
1. ψ is finite inside the box where V = 0 at 0 < x < a

2. ψ is zero outside the box, where V = ∞ i.e., x = 0 or x = a

The schrödinger’s equation for particle in a box is given by
d2 ψ 2mEψ
+ =0 (9)
dx2 h̄2

d2 ψ
2
+ k2ψ = 0 (10)
dx

2mE
k2 = (11)
h̄2
The general solution of this differential equation is of the form

ψ(x) = A sin kx + B cos kx (12)

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where A and B are arbitrary constants which are to be determined using boundary
conditions.
At x = 0, ψ = 0 , A and B are constants to be evaluated. Since cos 0 = 1, the
second term cannot describe the particle because it does not vanish at x = 0. Hence
we conclude that B = 0. Since sin = 0, the sine term always yields ψ = 0 at x = 0
as required. The above equation becomes ψ(x) = A sin kx.
At x = a, ψ = 0, only when ka = nπ, where n = 1, 2, 3.....

ψ(a) = A sin ka = 0

ka = nπ
nπ
k=
a

n2 π 2
k2 = (13)
a2
But
2mE
k2 = (14)
h̄2
Therefore, comparing equation(13) and (14), we get

2mE n2 π 2
=
h̄2 a2

n2 π 2 h̄2
En = (15)
2ma2

n2 h 2
En = (16)
8ma2

The En ’s are called energy eigen values of the particle in a box. When,

h2
n = 1, E1 =
8ma2

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Energy of the particle in ground state. Also known as Zero point energy of the
system.
h2
n = 2, E2 =
2ma2
Energy of the particle in first excited state and so on.
Normalization of wave function is given by
Z ∞
|ψ|2 dV = 1
−∞

We have,
 nπx 
ψn (x) = A sin (17)
a
Z a  nπx 
A2 sin2 dx = 1
0 a
Z a   
2 1 2nπx
A 1 − cos dx = 1
0 2 a
Z a  Z a   
2 1 2 2nπx
A dx − A cos dx = 1
0 2 0 a

A2
   
a  a  2nπx a
x − sin =1
2 0 2nπ a 0

A2 a
=1
2
r
2
A= (18)
a
Substituting the value of A in equation(17), we get
r
2  nπx 
ψn = sin (19)
a a
The normalized wave function of a particle in one dimensional box are called Eigen
function ψn .

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|y|
2
n=3 y
3
n=3
3
a/6 3a/6 5a/6

|y|
2
n=2 y
2
n=2
2

a/4 3a/4

|y| 2
n=1 y
1
n=1
1

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

x=0 x=0

Significance
The probability changes with n. But classical theory predicts same probability for
particle any where inside the box. The energy values of the bound particles are
quantized.

Expression for energy of free particle

A particle moving with no forces acting on it in any region of space is known as “free
particle”. That is F = 0 and so the potential energy, V(x) = constant for all x. We are
free to choose the constants to be zero, since the potential energy is determined only
within an arbitrary constant. The general time independent schrödinger equation is

d2 ψ 2m(E − V )ψ
+ =0 (20)
dx2 h̄2
Since V=0, equation(20) becomes

d2 ψ 2mEψ
+ =0 (21)
dx2 h̄2
The momentum of a particle is related to wave number of its de Broglie wave as

p = h̄k (22)
we know that
h
p= (23)
λ

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2π
k=
λ
or
2π
λ= (24)
k
Substituting (24) in (23), we get equation (22)

hk
p= = h̄k
2π
Therefore,

p2 = 2mE = h̄2 k 2

2mE
k2 = (25)
h̄2
Now equation(21) becomes
d2 ψ
2
+ k2ψ = 0 (26)
dx
Rearranging equation(25), we get

k 2 h̄2
E= (27)
2m

The above equation gives the energy eigen values of a free particle. The values are
continuous with k 2 always positive. The values of energy En for which schrödinger’s
steady state equation can be solved are called Eigen values and the corresponding
wave functions ψn are called eigen functions.

Problems
1. An electron is bound in an one dimensional potential well of width 1Åof infi-
nite wall height. Find its energy values in the ground state and also in the first
excited state.

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2. An electron is confined to move between two rigid wall separated by 20 Å. Find
the de-Broglie wavelength representing the first two allowed energy states of
the electron and the corresponding energies. Assuming the potential is zero.

3. An electron is trapped in a one dimensional potential well of width 0.1 nm.

Calculate its wavelengths and energies corresponding to first two excited states.

4. A quantum particle confined to one dimensional box of width a is in its first

excited

state. What is the probability of finding the particle over an interval
of a2 marked symmetrically at the center of the box.

5. A Quantum particle confined to one dimensional potential well of width ‘a’ is

in its first excited state. What is the probability of finding the
h particle over an
a ai
interval of marked at the first half of the potential well. 0 to
2 2
6. A particle confined in one dimensional potential well of infinite height and
width ‘a’ is in its first excited state. Calculate
ha i the probability of occupation in
the latter half of the potential well. to a
2
7. A quantum particle confined to one dimensional box of width a is in its first
excited state. What is the probability of finding the particle over an interval
a a 3a
of marked symmetrically at the center of the box. to
2 4 4

Questions
1. Explain properties of wave function.

2. Derive the expression for eigen value and eigen function for a particle in one
dimensional potential well.

3. Find the eigen values and eigen functions for a particle in one dimensional
potential well of infinite height.

4. Explain the significance of wave function. Mention any three properties of wave
function.

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5. Explain the significance of wave function and setup time independent Schrödinger’s
wave equation for particle in one dimensional motion.

6. Using schrödinger’s wave equation, show that energy values of a free particle
are continuous.

7. Derive steady state form of Schrödinger’s wave equation.

8. Why a wavefunction is physically insignificant.

9. Derive the time independent Schrödinger wave equation in one dimension and
discuss the case of a free particle.

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