Chapter 6

Quantum Mechanics

6.1 Schrödinger’s Wave Equation

From the preceding chapters it became clear that a new set of equations
is needed to describe the wave motion of particles; i.e. a wave equation is Erwin Schrödinger (1887-
1961) was a theoretical and
needed so that the wave function Ψ will be found that will allow us to experimental physicist in Vi-
calculate the probable values of the particle’s position, energy, momentum enna, Zrich and Berlin and
a significant contributor to
and so on. the wave theory of matter.
A plane wave traveling in the x -direction with velocity v having a wave- He mathematically devised
an equation of wave me-
length λ and frequency f can be represented as: chanics that bears his name.
Schrödinger’s research was
 x interrupted by two world
Ψ1 = A cos ω t − , ω = 2πf, v = λf
v  wars, but he nonetheless ad-
vanced quantum theory and

2πx
= A cos ωt − color theory. In 1933 he
λ was a co-recipient of the No-
bel Prize for physics. Today
To represent a complex wave, let he is popularly known for
the paradox of Schrödinger’s
  Cat.
2πx
Ψ2 = −jA sin ωt −
λ
   
2πx 2πx
∴ Ψ = Φ1 + Ψ2 = A cos ωt − − jA sin ωt −
λ λ
2πx
⇒ Ψ = Ae−j (ωt− λ ) (6.1)
But E = hf , λ = h/p and

2πx  x  2π
ωt − = 2π f t − = (Et − px)
λ λ h
1
Ψ = Ae−j ~ (Et−px) (6.2)
§6.2 is the mathematical description of the wave equivalent of an unrestricted
particle of total energy E and momentum p moving in +x-direction.

1
 Class Notes on
6.1. SCHRÖDINGER’S WAVE EQUATION Applied Modern Physics ECEG-2101

To get the fundamental differential equation in Ψ for a generally restricted

particle, differentiate §6.2 twice with respect to x,

∂2Ψ p2
= − Ψ (6.3)
∂x2 ~2

and differentiate §6.2 with respect to t

∂Ψ EΨ
= −j (6.4)
∂t ~

The total energy E (assuming non-relativistic)

E = Ek + Ep
p2
E = + Ep (6.5)
2m

Multiplying all terms in §6.5 by Ψ, we have

p2 Ψ
EΨ = + Ep Ψ (6.6)
2m

From §6.3 and §6.4,

∂2Ψ
p2 Ψ = −~2 (6.7)
∂x2
∂Ψ
EΨ = j~ (6.8)
∂t

Substituting these expressions in §6.6, we get the time-dependent form of

Schröinger’s equation for a particle of energy E moving in a potential Ep in
one dimension,

∂Ψ(x, t) ~2 ∂ 2 Ψ(x, t)
j~ =− + Ep Ψ(x, t) (6.9)
∂t 2m ∂x2

In three dimension, §6.9 becomes

~2 ∂ 2 ∂2 ∂2
 
∂Ψ(x, y, z, t)
j~ =− + + Ψ(x, y, z, t)+Ep Ψ(x, y, z, t), or
∂t 2m ∂x2 ∂y 2 ∂z 2

∂Ψ(x, y, z, t) ~2 2
j~ =− ∇ Ψ(x, y, z, t) + Ep Ψ(x, y, z, t) (6.10)
∂t 2m

Murad Ridwan, 2 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.2. TIME-IND. WAVE EQUATION Applied Modern Physics ECEG-2101

6.2 Time-Independent Schrödinger Wave Equation

In many cases, the potential energy is a function of space positions only, so
the wave amplitude §6.2 can be split into two independent parts- the space
and time dependent functions
1
Ψ(x, t) = Ae−j ~ (Et−px)
Et px
= Ae−j ~ ej ~
Et
= ψ(x)e−j ~ (6.11)
px
where ψ(x) = Aej ~ .
By substititing §6.11 in §6.9, we have the steady-state form of Schrödinger’s
equation
d2 ψ(x) 2m
+ (E − Ep )ψ(x) = 0 (6.12)
dx2 ~
In three dimension, it becomes
2m
∇2 ψ(x, y, z) + (E − Ep )ψ(x, y, z) = 0 (6.13)
~

Exercise 6.1 : The wave equation must be linear so that the superposition principle
can be applied to form wave packets using many waves. Prove that §6.9 is linear
by showing that it is satisfied for the wave function
Ψ(x, t) = aΨ1 (x, t) + bΨ2 (x, t)

where a and b are constants and Ψ1 and Ψ2 describe two waves each satisfying
§6.9.

6.3 Normalization and Probability

The probability p(x)dx of a particle being between x and x + dx is
p(x)dx = Ψ(x, t)Ψ∗ (x, t)dx (6.14)
The probability of the particle being between x1 and x2 is given by
Z x2
P = ΨΨ∗ (6.15)
x1

The wave function must also be normalized so that the probability of the
particle being somewhere on the x-axis is unity.
Z ∞
ΨΨ∗ dx = 1 (6.16)
−∞

Example 6.1: Normalize the wave function Ae−α|x| and find the probabilities of
the particle being between 0 and 1/α, and between 1/α and 2/α.

Murad Ridwan, 3 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.4. OPERATORS Applied Modern Physics ECEG-2101

6.4 Operators

An operator is any mathematical entity which operates on any function and

turns it into another function.

Example 6.2: Find Âψ(x) if the operator  is given by

1. Â(x) = x

∂ ∂2
2. Â( )=
∂x ∂x2

∂ ∂
3. Â(x, )= x
∂x ∂x

∂
Example 6.3: If Â(x, )un (x) = an un (x), an is called the eigenvalue and un (x)
∂x
∂ ∂
the eigenfunction. Find un (x) and an for the operator Â(x, ) = −j with
∂x ∂x
boundary condition that un (x) is periodic in the range L.

Exercise 6.2 : Establish the operator

∂ ∂
= nxn−1 + xn
∂xn ∂x

h i
Exercise 6.3 : The commutator of two operators is defined as Â, B̂ = ÂB̂ − B̂ Â.
 
∂ n
Show that , x = nxn−1
∂x
∂ ∂n
 
Exercise 6.4 : Evaluate , n
∂x ∂x
1 2
−2x
Exercise 6.5 : Show that
 un (x) = e is an eigenfunction of the operator
2
∂ ∂ 2
Â(x, )= −x
∂x ∂x2

Exercise 6.6 : Verify the operator equations

∂2
  
∂ ∂
+x −x = − x2 − 1
∂x ∂x ∂x2
∂2
  
∂ ∂
−x +x = − x2 + 1
∂x ∂x ∂x2

Murad Ridwan, 4 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.4. OPERATORS Applied Modern Physics ECEG-2101

The Momentum Operator p̂

2πx
Consider Ψ(x, t) = e−j(ωt− λ
)
= e−j(ωt−kx)

∂Ψ
= jke−j(ωt−kx) = jkΨ
∂x
2π 2π p
since k = = =
λ h/p ~
∂Ψ p
∴ = j Ψ
∂x ~
∂Ψ
⇒ pΨ = −j~
∂x

The momentum operator p̂ is therefore

∂
p̂ = −j~ (6.17)
∂x

The Energy Operator Ê

Again consider Ψ(x, t) = e−j(ωt−kx)

∂Ψ E E
= −jωΨ, but ω = 2πf = 2π( )=
∂t h ~
∂Ψ E
⇒ = −jΨ
∂t ~
∂Ψ
EΨ = j~
∂t

Therefore
∂
Ê = j~ (6.18)
∂t

Note:

• The position x is its own operator, i.e. x̂ = x

• To every observable there corresponds an operator

Example 6.4: Use the momentum and energy operators with the conservation of
energy to determine the Schrödinger wave equation.

Example 6.5: Obtain the relativistic form of Schrödinger equation.

Murad Ridwan, 5 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.5. EXPECTATION VALUES Applied Modern Physics ECEG-2101

6.5 Expectation Values

The wave function is used to determine values of the measurable quantities
like position, momentum and energy.
If we make many measurements of a particle along the x-axis, say N1 times
at x1 , N2 times at x2 , Ni times at xi , and so on, then the average value or
expectation value of x denoted by hxi is

N1 x1 + N2 x2 + · · · + Ni xi + · · ·
hxi =
N + N2 + . . . + Ni + · · ·
P 1
Nx
= Pi i i
i Ni

changing to continuous variable

R∞
xp(x) dx
hxi = R−∞
∞ , or
−∞ p(x) dx
R∞
xΨ∗ (x, t)Ψ(x, t) dx
hxi = R−∞
∞ ∗
(6.19)
−∞ Ψ (x, t)Ψ(x, t) dx

If the wave function is normalized

Z ∞
hxi = xΨ∗ (x, t)Ψ(x, t) dx (6.20)
−∞

Generally, the expectation value of any function g(x) for normalized wave
function Ψ(x, t) is
Z ∞
hg(x)i = Ψ∗ (x, t)g(x)Ψ(x, t) dx (6.21)
−∞

Any measurable quantity for which we can calculate the expectation value
is called a physical observable (e.g. position, linear momentum, angular mo-
mentum, energy, etc. ) Each of the physical observable has an associated
operator that is used to find the observable’s expectation value. In order to
compute the expectation value of some physical observable A, the operator
 must be placed between Ψ∗ and Ψ so that it operates on Ψ;
Z ∞
hAi = Ψ∗ (x, t)ÂΨ(x, t) dx (6.22)
−∞

For example, the expectation value hEi of the energy is

Z ∞
∂Ψ(x, t)
hEi = j~ Ψ∗ (x, t) dx
−∞ ∂t

Murad Ridwan, 6 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.6. PARTICLE IN RIGID BOX Applied Modern Physics ECEG-2101

6.6 Particle in Infinite Rectangular Potential Well

Consider a particle trapped in a rectangular one dimensional box (fig ) 6.1
so that it is constrained to move along the x-axis subject to:

∞, x ≤ 0, x ≥ L;
Ep = V (x) = (6.23)
0, 0 < x < L.

Figure 6.1: Particle in a rigid one-dimensional box

§6.12 becomes

d2 ψ(x) 2m
+ (E − V )ψ(x) = 0
dx2 ~

Case 1: x < 0 or x > L.

V = ∞ ⇒ ψ = 0 i.e. there is zero probability for the particle to be
observed in x < 0 or x > L.

Case 2: 0 < x < L

r
d2 ψ(x) 2mE 2mE
2
+ ψ = 0, let k =
dx ~ ~
d2 ψ(x)
⇒ + k2 ψ = 0
dx2
∴ ψ(x) = A sin kx + B cos kx

The wave function must be continuous;

ψ(x)|x=0,L = 0
⇒ ψ(x = 0) = B = 0
ψ(x = L) = A sin kL = 0

Murad Ridwan, 7 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.6. PARTICLE IN RIGID BOX Applied Modern Physics ECEG-2101

A = 0 leads to trival solution; we must have

kL = nπ, n = 1, 2, . . .
 nπx 
∴ ψn (x) = A sin , n = 1, 2, . . .
L
Z ∞
but ψn∗ ψn dx = 1
−∞
Z L  nπx 
⇒ A2 sin2 dx = 1
0 L
L
⇒ A2 = 1
2 r
2
⇒A =
L
Therefore, the normalized wave function is
r
2  nπx 
ψn (x) = sin , n = 1, 2, 3, . . . (6.24)
L L

Since kL = nπ,
r
nπ 2mEn
kn = =
L ~2
2 2
π ~ 2
⇒ En = n , n = 1, 2, 3, . . . (6.25)
2mL2
From §6.25, the possible energies En of the particle, called the energy levels,
are quantized. n is called the quantum number. The lowest energy level
(n = 1) is called the ground state.

π 2 ~2
E1 =
2mL2

Example 6.6: Find En for (a) an electron in a box 1 Å wide and (b) a rock 0.5 kg
in a box 1 m wide. Discuss the results.

Example 6.7: For the infinite rectangular potential well, find the probability that
a particle while in its ground state is in each third of the one-dimensional box, i.e.
0 ≤ x ≤ L/3, L/3 ≤ x ≤ 2L/3, and 2L/3 ≤ x ≤ L.

Example 6.8: Determine the expectation values for x, x2 , p, and p2 of a particle in

an infinite rectangular well for the first excited state.

Example 6.9: Calculate the transition energy from the first excited to the ground
state for a proton confined to the nucleus (typical radius of nucleus ≈ 10−14 m).
Use the infinite rectangular well model.

Murad Ridwan, 8 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.7. PARTICLE IN NON-RIGID BOX Applied Modern Physics ECEG-2101

Exercise 6.7 : An electron moves with a speed v = 10−3 c inside a one-dimensional

box (Ep = 0) of length 9.7 nm. The potential is infinite elsewhere. What approxi-
mate quantum number does the electron posses? (Answer : n = 8)

Exercise 6.8 : What is the minimum energy of (a) a proton and (b) an α-particle
trapped in a one-dimensional region the size of a uranium nucleus (radius = 7 ×
10−15 m)?

6.7 Finite Rectangular Potential Well


 Vo , x ≤ 0; region I
V (x) = 0, 0 < x < L; region II (6.26)
Vo , x ≥ L. region III


with Vo > E.

Figure 6.2: Particle in a non-rigid one-dimensional box

Case 1: In regions I and III

d2 ψ 2m
+ 2 (E − Vo )ψ = 0
dx2 ~
2m
Let γ 2 = (E − Vo )
~2
d2 ψ(x)
∴ = γ 2 ψ(x)
dx2
⇒ ψ(x) = Ceγx + De−γx

for x < 0 (region I):

ψI (x) = Ceγx (set D = 0 because De−γx → ∞.) (6.27)

for x > L (region III):

ψIII (x) = De−γx (6.28)

Murad Ridwan, 9 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.8. THE HARMONIC OSCILLATOR Applied Modern Physics ECEG-2101

Case 2: Inside the well, Vo = 0

r
d2 ψII 2 2mE
2
= −k ψII , k =
dx ~2
⇒ ψII = Aejkx + Be−jkx , 0 < x < L (6.29)
Apply the boundary conditions and normalization to get A, B, C, and D
ψI (x = 0) = ψII (x = 0)
ψII (x = L) = ψIII (x = L)

6.8 The Harmonic Oscillator

Harmonic motion occurs when a system vibrates about an equilibrium con-
figuration.
Consider the system in fig 6.3;

Figure 6.3: The Harmonic Oscillator

d2 x
m = −µx
dt2
d2 x µ µ
⇒ 2 + x = 0, let ω 2 =
dt m m
d2 x
⇒ 2 + ω2x = 0
dt
⇒ x = A cos ωt, A − maximum amplitude
Potential energy of the particle is the work done to bring the particle from
x = 0 to x = x against the restoring force Fr .
Z x Z x
1
Ep = V (x) = − Fr (x) dx = + µx dx = µx2
0 0 2
The total energy of the oscillator is E = 12 µA2 and (classically) can have
any value.
Schrödinger’s equation for the harmonic oscillator (Ep = 12 µx2 ) becomes
d2 ψ 2m
 
1 2
+ 2 E − µx ψ = 0
dx2 ~ 2
2
 
d ψ 2mE mµ 2
⇒ + − 2 x ψ = 0 (6.30)
dx2 ~2 ~

Murad Ridwan, 10 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.8. THE HARMONIC OSCILLATOR Applied Modern Physics ECEG-2101

d2 ψ mµ d2 ψ
r r
2 mµ 2
Let y = x , then = . §6.30 becomes
~2 dx2 ~2 dy 2

d2 ψ
 
2E
+ − y ψ = 0, where ω 2 = µ/m
2
(6.31)
dy 2 ~ω
Let us try a solution of the form
1 2
ψ(y) = f (y)e− 2 y (6.32)

then §6.31 becomes

d2 f
 
df 2E
2
− 2y + −1 f = 0
dy dy ~ω
2E
set − 1 = 2n (6.33)
~ω
d2 f (y) df (y)
∴ 2
− 2y + 2nf (y) = 0 (6.34)
dy dy
This is a standard mathematical equation known as Hermite’s Equation.
The solution to it are called Hermite’s Polynomials, given by:
2 dn −y2
f (y) = Hn (y) = (−1)n ey e , n = 0, 1, 2, . . . (6.35)
dy n
The eigenfunctions of the harmonic oscillator, therefore, are

Table 6.1: Some Hermite Polynomials

n Hn (y) En
1
0 1 2 ~ω
3
1 2y 2 ~ω
2 5
2 4y − 2 2 ~ω
3 7
3 8y − 12y 2 ~ω
4 2 9
4 16y − 48y + 12 2 ~ω
5 3 11
5 32y − 160y + 120y 2 ~ω

1 2
ψn (y) = AHn (y)e− 2 y

where A is the normalization constant and is given by

 1
2mf 4 ω
A= (2n n!), where f = is the frequency of oscillation.
~ 2π

 1
2mf 4 1 2
∴ ψn (y) = (2n n!)Hn (y)e− 2 y (6.36)
~

Murad Ridwan, 11 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.
 Class Notes on
6.8. THE HARMONIC OSCILLATOR Applied Modern Physics ECEG-2101

From §6.33, the energy levels are given by

2E
− 1 = 2n
~ω
 
1
⇒ En = n + ~ω (6.37a)
2
 
1
or En = n + hf (6.37b)
2

The probability of finding the object at x is depicted in fig. 6.9. It is obvious

that the disagreement between the classical and quantum mechanical results
reduce as n increases. This is a consequence of the correspondence principle.

Murad Ridwan, 12 of 12
Dep. of Electrical & Computer Engineering
FOT, Addis Ababa University.