Chapter 6: Quantum Mechanics

Chapter 6: Quantum Mechanics

6.1. Introduction

6.2. Schrödinger's wave equation: Time dependent form

6.3. Schrödinger's wave equation: Time independent form (steady state form)

6.4. Operators

6.5. Probability, normalization and expectation values

6.6. Particle in an infinite rectangular potential wall

6.7. Finite rectangular potential well: (particle in a non-rigid box)

6.8. The harmonic oscillator (quantum oscillator)

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Chapter 6: Quantum Mechanics

6.1. Introduction

In spite of the fact that the Bohr’s atomic model and spectral lines gives satisfactory results for hydrogen atom,
it suffers from some serious defects:

1. It can be applied to only hydrogen and hydrogenic atoms. It fails for most other complex atoms.

2. It fails to explain the fine structure of even hydrogen atoms. (Latter explained by Sommerfield.)

3. It fails to explain the relative variation of intensities of the spectral lines.

4. It could not explain the appearance of a large number of spectral lines when the source is placed under
the effect of an electric and magnetic fields (Stark and Zeeman effects, respectively.)

5. It could not explain the binding of atoms into molecules as well as the how individual atoms interact
with another.

An approach emphasizing an atomic phenomenon of generality than Bohr’s theory was developed in 1925-
1926 by Erwin Schrödinger, Werner Heisenberg and others under the apt name of “Quantum mechanics”
which contributed to the understanding of nuclei, atoms, molecules and matter in the solid state.

By early 1930s, the application of quantum mechanics to problems involving nuclei, atoms, molecules and
matter in the solid state made it possible to understand a vast body of otherwise puzzling data ( a vital
attribute of any theory) and led to predictions of remarkable accuracy.

Quantum mechanics & Newtonian mechanics

The fundamental difference between Newtonian mechanics and quantum mechanics lies in what it is that
they describe.

Newtonian mechanics takes for granted that a particle’s mass, position, velocity, acceleration, etc can be
deterministically measured which is valid since its predictions of observable magnitudes of moving bodies
agree with the measured values of those magnitudes.

Quantum mechanics, also consists of relationships between observable magnitudes of quantities which are
probabilistic in the atomic ream due to the uncertainty principle. For instance, instead of asserting the ground
state electron’s orbit radius of hydrogen to be exactly 5.3 x 10-11m, as the Bohr theory does, quantum
mechanics states it is the most probable radius.

Newtonian mechanics is an approximate version of quantum mechanics for macroscopic bodies. Since
macroscopic bodies consist of so many individual atoms, departures from average behavior are unnoticeable
which accounts for the illusory certainties proclaimed by Newtonian mechanics.

Thus, instead of two sets of physical principles, one for the macroscopic universe and one for the microscopic
universe, there is only a single set, and quantum mechanics represents our best effort to date in formulating it.

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Chapter 6: Quantum Mechanics

6.2. Schrödinger’s Wave Equation: Time dependent form

In quantum mechanics, the wave nature of a particle/body is considered in which only the probabilistic
magnitudes of quantities associated to the particle such as position, momentum, energy, etc are determined
using the wave equation Ψ of the particle.

Quantum mechanics is thus concerned mainly with the determination of the wave function Ψ of a particle
when its freedom of motion is limited/restricted by the action of external forces.

While Ψ itself has no physical interpretation (not measurable), Ψ2 (or Ψ Ψ*=|Ψ|2 if Ψ is complex) evaluated at
a specific point and at a specific instant is proportional to the probability P of experimentally finding the
particle at the point at that instant.

Ψ should satisfy the following properties

i. Since 𝑃 ∝ Ψ , 0 < ∫ Ψ 𝑑𝑣 < ∞ [i.e. the probability of finding the particle over all space must be
finite if the particle is a real body]

0 → 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑑𝑜𝑒𝑠𝑛 𝑡𝑒𝑥𝑖𝑠𝑡 𝑎𝑛𝑦𝑤ℎ𝑒𝑟𝑒

ii. If ∫ Ψ 𝑑𝑣 =
∞ → 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑒𝑥𝑖𝑠𝑡𝑠 𝑎𝑛𝑦𝑤ℎ𝑒𝑟𝑒 𝑠𝑖𝑚𝑢𝑙𝑡𝑎𝑛𝑒𝑜𝑢𝑠𝑙𝑦

iii. Ψ > 0 and real

iv. Ψ should be single valued since P is so. (i.e. p is also single valued at a specific point and instant)

v. Ψ, , , must be continuous everywhere

Schrödinger’s equation, which is the fundamental equation of quantum mechanics in the sense that Newton’s
2nd law of motion is the fundamental equation of classical mechanics, is a wave equation is in the variable Ψ
for a particle whose freedom of motion is limited by the action of external forces. [If no external forces, no
need of Schrödinger’s equation to describe the motion!]

A (free/unrestricted) plane wave (in the x- Ψ plane) travelling in the x-direction with velocity v, having a wave
length λ and frequency f can be represented by:

Ψ(𝑥, 𝑡) = 𝐴𝑐𝑜𝑠𝜔 𝑡 − = 𝐴𝑐𝑜𝑠 𝜔𝑡 − 𝑥 …… Unrestricted wave

where 𝑣 = 𝜆𝑓, 𝜔 = 2𝜋𝑓

Note: A free wave (free particle) is one that on which no external force is applied.

Such a wave is only one solution of a differential equation generally governing any plane wave (derived from
the physics of the actual situation) of the form

= …………… 6.1

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Chapter 6: Quantum Mechanics

The portion of the entire solution of this wave equation for waves in the +x-direction becomes:

Ψ(x, t) = A𝑒 = A𝑒 …….. 6.2

If Ψ represents the vertical displacement of a vibrating string, only the real part will have significance and the
imaginary part must be discarded.

Concerning wave motion of a body, though the complex Ψ meaningless (is not in itself a measureable
quantity), ΨΨ ∗ will have meaning.

Since E = hf and λ =

2𝜋 𝑥 2𝜋
𝜔𝑡 − 𝑥 = 2𝜋 𝑓𝑡 − = (𝐸𝑡 − 𝑝𝑥)
𝜆 𝜆 ℎ
then

( )
Ψ(x, t) = A𝑒 ℏ …. 6.3

Equation 6.3. is the mathematical description of the wave equivalent of an unrestricted particle (if freely
moving particles) of total energy E and momentum p moving in the +x- direction.

In quantum mechanics, we are, however, most interested in situations where the motion of a particle is
restricted.

Fig. A standing wave

For instance,

i) A standing wave which occurs in a vibrating string of finite length fastened at both ends due to two
waves propagating in the +x and –x directions simultaneously

ii) An electron bound to an atom by the electric field of the nucleus is restricted.

To get the fundamental differential equation in Ψ for a generally restricted particle, which we solve in specific
situations (restrictions), we differentiate equation 6.3 twice w.r.t. x yielding
𝒑
=− Ψ …… 6.4
ℏ

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Chapter 6: Quantum Mechanics

and once w.r.t. t yielding

= −𝑗 Ψ …..6.5
ℏ

Under the action of external forces, the total energy of a particle in non-relativistic case is the sum of its K.E.
and P.E. i.e

𝐸 = 𝐸 +𝐸 = + 𝑉 ….. 6.6

Multiplying both sides of Eqn 6.6. by the wave function Ψ,

𝒑
𝐸Ψ = Ψ + 𝑉Ψ ….. 6.7

From Eqns 6.4 and 6.5 we see

𝑝 Ψ = −ℏ ………6.8.

𝐸Ψ = 𝑗ℏ …………..6.9

Substituting 6.8 & 6.9 into 6.7 we get the time-dependent form of Schrödinger’s equation for a particle of
energy E moving in a potential V in one dimension,
( ,) ℏ ( ,)
𝑗ℏ =− + 𝑉Ψ(x, t) …… 6.10

In three dimensions (3D), the time dependent form of Schrödinger’s equation becomes
( , , ,) ℏ
𝑗ℏ =− + + Ψ(x, y, z, t) + 𝑉Ψ(x, y, z, t)

or
ℏ
𝑗ℏ =− ∆ Ψ + 𝑉Ψ ……… 6.11

where Ψ = Ψ(x, y, z, t) and V = V(x, y, z, t)

Any restrictions that may be present on the particle’s motion will affect the potential energy function V.

Once V is known, Schrödinger's equation (Eqns 6.10 or 6.11) may be solved for Ψ of the particle, from which
its probability density function Ψ may then be determined for a specified x,y,z,t.

6.3. Schrödinger's wave equation: Time independent case (steady state form)

In many problems, the potential energy V of a particle doesn’t depend on t explicitly; the forces on the particle
and hence its P.E. vary with position only.

When this is the so, Eqn 6.9 may be simplified by removing all reference to t.

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Chapter 6: Quantum Mechanics

We see that Ψ(x, t) in Eqn 6.3 can be decomposed (split) into two independent parts – space dependent
function Ψ(x) and time dependent function Ψ(t), i.e.

( )
Ψ(x, t) = A𝑒 ℏ = A𝑒 ℏ .𝑒 ℏ = Ψ(x). 𝑒 ℏ = Ψ(x)Ψ(t) ….6.12

where

Ψ(x) = A𝑒 ℏ and Ψ(t) = 𝑒 ℏ

As it happens, the time variations of all functions of particles acted upon by stationary forms have the same
form as that of as unrestricted particles.

Substituting Eqn 6.12 in to 6.10

𝐸 ℏ 𝑑 Ψ(x)
𝑗ℏ −𝑗 Ψ(x). 𝑒 ℏ =− .𝑒 ℏ + 𝑉Ψ(x). 𝑒 ℏ
ℏ 2𝑚 𝑑𝑥
or
( )
+ (𝐸 − 𝑉)Ψ(x) = 0 …. 6.13
ℏ

From Eqn 6.6, (E- V) is the K.E.

In three dimensions, the steady state Schrödinger equation becomes:

+ + + (𝐸 − 𝑉)Ψ(x) = 0
ℏ

Or

∆ Ψ(𝑥, 𝑦, 𝑧) + (𝐸 − 𝑉)Ψ(x, y, z) = 0 …… 6.14

ℏ

Exercise:

The wave equation must be linear so that the superposition principle can be applied to form wave packets
using many waves. Prove that Eqn 6.10 is linear by showing that it satisfies for the wave function:

Ψ(𝑥, 𝑡) = 𝑎Ψ (𝑥, 𝑡) + 𝑏Ψ (𝑥, 𝑡)

where a, b are constants and & describe two waves each satisfying Eqn 6.10.

6.4. Operators

An operator is any mathematical entity which operates on any function and turns it into another function

Fig. A mathematical operation process

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Chapter 6: Quantum Mechanics

6.4.1. The momentum operator 𝑝̂

( )
Consider Ψ(x, t) = A𝑒 = A𝑒

Then,
𝜕Ψ ( )
= 𝑗𝐴𝑘𝑒 = 𝑗𝑘Ψ
𝜕𝑥

Since 𝑘 = = = ,
ℏ

Then = 𝑗 Ψ or 𝑝Ψ = −jℏ
ℏ

Therefore, the momentum operator becomes:

𝑝 = −jℏ …….…6.15

6.4.2. The energy operator 𝐸

( )
Again, consider Ψ(x, t) = A𝑒

From which

𝜕Ψ
= −𝑗𝜔Ψ
𝜕𝑡

But 𝜔 = 2𝜋𝑓 = 2𝜋 =
ℏ

Thus, = −𝑗 Ψ
ℏ

Therefore, the energy operator becomes

𝐸 = jℏ …6.16

Note:

 To every observable there corresponds an operator.

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

Exercises:

1. Find 𝐴 Ψ(𝑥) if the operator 𝐴 is given by

A. 𝐴 (𝑥) = 𝑥
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Chapter 6: Quantum Mechanics

B. 𝐴 =

C. 𝐴 𝑥, = 𝑥

2. If 𝐴 𝑥, 𝑢 (𝑥) = 𝑎 𝑢 (𝑥), 𝑎 is called the eigen value and 𝑢 (𝑥) the Eigen function. Find 𝑢 (𝑥) and

𝑢 for the operator 𝐴 𝑥, = −𝑗 with boundary condition that 𝑢 (𝑥) is periodic in the range L.

3. Establish the operator

𝜕𝒏 𝜕
= 𝑛𝑥 +𝑥
𝜕𝑥 𝜕𝑥
4. The commutator of two operators defined as [𝐴, 𝐵 ] = 𝐴 𝐵 − 𝐵 𝐴 .

Show that ,𝑥 = 𝑛𝑥

5. Evaluate ,

6. Show that 𝑢 (𝑥) = 𝑒 is an Eigen function of the operator 𝐴 𝑥, = −𝑥

7. Verify the operator equations:

i. +𝑥 −𝑥 = −𝑥 −1

ii. −𝑥 +𝑥 = −𝑥 +1

8. Use the momentum and energy operators with the conservation of energy to determine the
Schrödinger wave equation.

9. Obtain the relativistic form of Schrödinger wave equation.

6.5. Probability, normalization and expectation values

The wave function Ψ is used to determine the probabilistic values of measurable quantities such as position,
momentum and energy.

For instance, if a one dimensional probability density function p(x) is associated with the probable position x of
a particle (in restricted motion) in the x- axis, then the probability of the particle being between x and x + dx is

𝑝(𝑥)𝑑𝑥 = Ψ(x, t)Ψ ∗ (𝑥, 𝑡)𝑑𝑥 … 6.17

The probability of particle being between x2 > x1 is given by

𝑝(𝑥 < 𝑥 < 𝑥 ) = 𝑃 = ∫ 𝑝(𝑥)𝑑𝑥 = ∫ ΨΨ ∗ 𝑑𝑥 ….. 6.18

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Chapter 6: Quantum Mechanics

Since the probability of particle being somewhere on the entire x-axis is unity (0 ≤P ≤1), the wave function
must be normalized to account this: i.e

∫ ΨΨ ∗ 𝑑𝑥 = 1 …. 6.19

Example:
| |
Given a wave function Ψ(x) = A𝑒

i. Determine A for a normalized wave function.

ii. Determine the probability of particle being between

a) 0 and 1/α b) 1/α and 2/α

Solution

i) Normalization gives
∝| |
∫ ΨΨ ∗ 𝑑𝑥 = 1 or ∫ A 𝑒 𝑑𝑥 = 1

−𝑥 𝑓𝑜𝑟 𝑥 < 0
Since |𝑥| =
𝑥 𝑓𝑜𝑟 𝑥 > 0

∝| | ∝( ) ∝
A 𝑒 𝑑𝑥 = A 𝑒 𝑑𝑥 + 𝑒 𝑑𝑥

∝ ∝ [(1 − 0) + 1(0 − 1)] =

= A 𝑒 + 𝑒 = =1

From which 𝐴 = ±√𝛼

| | | | ∝| |
Thus, 𝑝(𝑥) = ΨΨ ∗ = ±√𝛼𝑒 . ±√𝛼𝑒 = 𝛼𝑒

ii) 𝑝(𝑥 < 𝑥 < 𝑥 ) = ∫ 𝑝(𝑥)𝑑𝑥 = ∫ ΨΨ ∗ 𝑑𝑥

∝| |
a) 𝑝 0 < 𝑥 < = ∫ 𝛼𝑒 𝑑𝑥 = 𝛼 ∫ 𝑒 ∝
𝑑𝑥 = 𝑒 ∝
= − (𝑒 − 1) =

or 𝑝 0<𝑥< = 0.43

∝| |
b) 𝑝 <𝑥< = ∫ 𝛼𝑒 𝑑𝑥 = 𝛼 ∫ 𝑒 ∝
𝑑𝑥 = 𝑒 ∝
= − (𝑒 −𝑒 )=

or 𝑝 <𝑥< = 0.06

Expectation values

Two distinct quantities associated with Ψ(x) are sharp and fuzzy quantities.

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Chapter 6: Quantum Mechanics

Example of a sharp quantity is E which is fixed by the quantum number n in stationary states leading to Ψ.

If we make many position measurements of a particle along the x-axis, say N1 times at t1, N2 times at t2, Ni
times at ti, and so on, the average value or expectation value of x denoted by <x> is given by:

𝑁 𝑥 + 𝑁 𝑥 + ⋯+ 𝑁 𝑥 + ⋯ ∑ 𝑁 𝑥
< x >= =
𝑁 + 𝑁 + ⋯+ 𝑁 + ⋯ ∑ 𝑁

If the measurement is done continuously (in an infinitesimally small spacing)

∫ 𝑥𝑝(𝑥)𝑑𝑥
< x >=
∫ 𝑝(𝑥)𝑑𝑥

or

∫ ( , ) ∗( , )
< x >= …. 6.20
∫ ( , ) ∗( , )

If the wave function is normalized,

𝛹𝛹 ∗ 𝑑𝑥 = 1

Thus,

< x >= ∫ 𝑥𝛹(𝑥, 𝑡)𝛹 ∗ (𝑥, 𝑡)𝑑𝑥 …. 6.21

Generally, the expectation of any function g(x) for a normalized wave function (𝑥, 𝑡) , is given by

< g(x) >= ∫ 𝛹 ∗ (𝑥, 𝑡)𝑔(𝑥)𝛹(𝑥, 𝑡)𝑑𝑥 ………... 6.22

Any measurable quantity for which we can calculate the expectation value is called physical observable. (e.g.
position, linear momentum, angular momentum, 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 𝐴 must be placed
between 𝛹 ∗ and 𝛹 so that it operates on 𝛹, i.e.

< A >= ∫ 𝛹 ∗ (𝑥, 𝑡)𝐴 𝛹(𝑥, 𝑡)𝑑𝑥 …. 6.23

For example, the expectation value < E > of the energy of a particle is
( ,)
< E >= jℏ ∫ 𝛹 ∗ (𝑥, 𝑡) 𝑑𝑥 …. 6.24

and the expectation value < P > of the momentum of a particle is

( ,)
< p >= −jℏ ∫ 𝛹 ∗ (𝑥, 𝑡) 𝑑𝑥
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Chapter 6: Quantum Mechanics

The quantum uncertainty, scatter from the mean value, in the particle’s position is measured by the standard
deviation 𝜎 of the observed data.

For discrete data,

∑(𝑥 − 𝑥̅ )
𝜎= = (𝑥 ) − (𝑥̅ )
𝑁

where
∑( ) ∑
(𝑥 ) = and 𝑥̅ =

If 𝜎 = 0, the data is sharp (i.e. all data identical to the average).

If 𝜎 ≠ 0, the data exhibits fuzziness or spread.

In quantum mechanics, the quantum uncertainty in position, denoted by ∆𝑥 (≡ 𝜎) is computed from.

∆𝑥 = < 𝑥 > −< 𝑥 >

which measures the degree of fuzziness of the position.

Example:

Compute a) the average position <x> and b) quantum uncertainty in this value ∆x for a particle in 1D box of
width L assuming a ground state.

Solution:

Recall 𝛹(𝑥) = 𝑠𝑖𝑛 , 0≤𝑥≤𝐿

0, 𝑒𝑙𝑠𝑒𝑤ℎ𝑒𝑟𝑒

i) Average position < x >= ∫ 𝑥𝛹 ∗ (𝑥)𝛹(𝑥)𝑑𝑥 = ∫ 𝑥𝑠𝑖𝑛 𝑑𝑥 = for n = 1

ii) ∆𝑥 = √< 𝑥 > −< 𝑥 >

2 𝜋𝑥 1 1
< 𝑥 >= 𝑥 𝛹 ∗ (𝑥)𝛹(𝑥)𝑑𝑥 = 𝑥 𝑠𝑖𝑛 𝑑𝑥 = 𝐿 −
𝐿 𝐿 3 2𝜋

and < 𝑥 > = =

Thus, ∆𝑥 = √< 𝑥 > −< 𝑥 > = − − = 0.181L

And thus 𝑥 = ± 0.181𝐿; thus, the whereabouts of the particle is largely unknown.

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Chapter 6: Quantum Mechanics

6.6. Particle in an infinite rectangular potential well

Consider a particle trapped in a rectangular box of width L so that it is constrained to move back and forth
between the infinitely rigid walls of the box in the x-axis.

Fig.: Particle in a rigid 1D box of infinite potential well

We would like to see

i) How Schrödinger equation is solved when the motion of the particle is subject to such restriction

ii) The character properties of solutions to this equation, such as quantization of the particle’s energy

iii) Comparison of predictions from quantum mechanics and Newtonian mechanics.

A particle doesn’t lose energy when it collides with rigid walls so that its total energy stays constant.

From the formal point of view of quantum mechanics, the potential energy V of the particle is ∞ on both sides
of the box, while V is constant (say 0 for convenience) on the inside.

We can state the problem as determining 𝛹(𝑥) from

𝑑 Ψ(x) 2𝑚
+ (𝐸 − 𝑉)Ψ(x) = 0
𝑑𝑥 ℏ
∞, 𝑥 ≤ 0, 𝑥 ≥ 𝐿
Subject to 𝑉(𝑥) = ………….. 6.25
0, 0 < 𝑥 < 𝐿
Case 1: 𝑥 ≤ 0, 𝑥 ≥ 𝐿 (E<<V)

Since the particle can’t have infinite total energy E, it can’t exist outside the box, and so its wave function
Ψ = 0 for 𝑥 ≤ 0 & 𝑥 ≥ 𝐿

i.e. the probability for the particle to be observed in 𝑥 ≤ 0 & 𝑥 ≥ 𝐿 is zero.

Case 2: 0 < 𝑥 < 𝐿

Here, V = 0 implying,

𝑑 Ψ(x) 2𝑚𝐸
+ Ψ(x) = 0
𝑑𝑥 ℏ
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Chapter 6: Quantum Mechanics

( )
Letting, 𝑘 = , + 𝑘Ψ(x) = 0
ℏ

Solving the differential equation for Ψ(x), we get

Ψ(x) = 𝐴𝑠𝑖𝑛𝑘𝑥 + 𝐵𝑐𝑜𝑠𝑘𝑥

Since Ψ(x) must be continuous (and from results of boundary conditions of Ψ(x) for case 1),

Ψ(x)| , =0

Thus, Ψ(0) = 𝐴𝑠𝑖𝑛0 + 𝐵𝑐𝑜𝑠0 = 0 from which B = 0

Ψ(L) = 𝐴𝑠𝑖𝑛𝑘𝐿 + 𝐵𝑐𝑜𝑠𝑘𝐿 = 𝐴𝑠𝑖𝑛𝑘𝐿 = 0

Since A = 0 leads to a trivial solution, we must have 𝑘𝐿 = 𝑛𝜋, 𝑛 = 1, 2, 3, …

Thus, 𝛹 (𝑥) = 𝐴𝑠𝑖𝑛 , n = 1, 2, 3,…

A can be determined from the normalization of the wave function.

Thus, ∫ 𝛹 ∗ (𝑥). 𝛹 (𝑥)𝑑𝑥 = 𝐴 ∫ 𝑠𝑖𝑛 𝑑𝑥 = 1

From which 𝐿 = 1 or 𝐴=

Thus, 𝛹 (𝑥) = 𝑠𝑖𝑛 , n = 1, 2, 3,… …6.26

[which is a Eqn of a standing wave]

a) 𝛹 (𝑥) b) 𝛹 (𝑥) [A a particular pt x, the prob. of the particle being present is different for different n]

Fig.: Standing waves

Since 𝑘𝐿 = 𝑛𝜋, 𝑘 = =
ℏ

From which,
ℏ
𝐸 = 𝑛 (n= 1, 2, 3, … ) ……. 6.27

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Chapter 6: Quantum Mechanics

Thus, the possible total energies En of the particle , called energy levels, are quantized.
ℏ
n is called the quantum number. The lowest energy level (n = 1) is called the ground state, i.e. 𝐸 =

The confinement of the particle leads to restrictions on its wave function that permit it to have only quantized
energies.

The particle can’t have zero (total) energy E in the box. Otherwise Ψ(x) = 0 everywhere in the box implying
the particle can’t be present in the box.

The exclusion of E = 0 as a possible value for the energy of a trapped particle (like the limitation of E to a
discrete set of definite values) is a quantum-mechanical result that has no counterpart in classical mechanics,
where all energies, including zero, are presumed possible.

Example 1: Find En for the motion of

a) an electron in a box 1A0 wide b) a 10 g marble ball in a box of 10 cm wide

Discuss the results

Solution:

. ×
ℏ .
×
a) 𝐸 = 𝑛 = )
𝑛 = 6 × 10 𝑛 𝐽 = 38𝑛 eV
× . × ×(

We see that, E1= 38 eV, E2 = 152 eV, E3 = 342 eV

The energy levels are sufficiently far apart to make the quantization of electron energy conspicuous.

. ×
ℏ .
×
b) 𝐸 = 𝑛 = )
𝑛 = 5.5 × 10 𝑛 𝐽 = 3.43 × 10 𝑛 eV
× × ×( ×

Thus, E1 = 3.43 × 10 eV, a K.E. with speed v = 3.3 x10-31 m/s which is experimentally
indistinguishable from a stationary marble!

If the marble to have a distinguishable velocity, v = (1/3) m/s, then n = 10 30 !

Thus, the permissible energy levels are very close together (i.e. continuous energy: for say n = 10 30 and
n = n+1 = 1030 +1) that there is no way of determining if the marble can take on only discrete energies.

Hence, in the domain of everyday experience, quantum mechanics effects are imperceptible which
accounts the seemingly success of Newtonian mechanics.

Example 2: For the infinite rectangular potential well, find the probability that a particle while in its ground
state is in each third of the 1D box.

i.e. i) 0 ≤ 𝑥 ≤ 𝐿/3 ii) 𝐿/3 ≤ 𝑥 ≤ 2𝐿/3 iii) 2𝐿/3 ≤ 𝑥 ≤ 𝐿

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Chapter 6: Quantum Mechanics

Solution

The normalized wave function if the particle becomes

2 𝑛𝜋𝑥
𝛹 (𝑥) = 𝑠𝑖𝑛 , 0≤𝑥≤𝐿
𝐿 𝐿
0, 𝑒𝑙𝑠𝑒𝑤ℎ𝑒𝑟𝑒
The probability that the particle exists between x1 and x2 where x1,x2 ε[0,L] is given by

𝑝(𝑥 ≤ 𝑥 ≤ 𝑥 ) = ∫ 𝑝(𝑥)𝑑𝑥 = ∫ ΨΨ ∗ 𝑑𝑥

= ∫ 𝑠𝑖𝑛 𝑑𝑥 [𝑠𝑖𝑛 𝑧 = ]

21 2𝑛𝜋𝑥
= (1 − 𝑐𝑜𝑠 )𝑑𝑥
𝐿2 𝐿

1 𝐿 2𝑛𝜋𝑥
= 𝑥− 𝑠𝑖𝑛
𝐿 2𝑛𝜋 𝐿

1 𝐿 2𝑛𝜋𝑥 1 𝐿 2𝑛𝜋𝑥
= 𝑥 − 𝑠𝑖𝑛 − 𝑥 − 𝑠𝑖𝑛
𝐿 2𝑛𝜋 𝐿 𝐿 2𝑛𝜋 𝐿
1 𝐿 2𝑛𝜋𝑥 2𝑛𝜋𝑥
= 𝑥 −𝑥 )+ (𝑠𝑖𝑛 − 𝑠𝑖𝑛
𝐿 2𝑛𝜋 𝐿 𝐿
In the ground state, n = 1
𝑥 −𝑥 1 2𝜋𝑥 2𝜋𝑥
𝑝(𝑥 ≤ 𝑥 ≤ 𝑥 ) = + 𝑠𝑖𝑛 − 𝑠𝑖𝑛
𝐿 2𝜋 𝐿 𝐿

For (i), 𝑝 0 ≤ 𝑥 ≤ = + 𝑠𝑖𝑛0 − 𝑠𝑖𝑛 = − 𝑠𝑖𝑛 = 0.195

(ii) 𝑝 ≤𝑥≤ = + 𝑠𝑖𝑛 − 𝑠𝑖𝑛 = 0.6089

(iii) 𝑝 ≤𝑥≤𝐿 = + 𝑠𝑖𝑛 − 𝑠𝑖𝑛2𝜋 = 0.195

(iv) 𝑝(0 ≤ 𝑥 ≤ 𝐿) = + [𝑠𝑖𝑛0 − 𝑠𝑖𝑛2𝜋] = 1 − 0 = 1.0

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Chapter 6: Quantum Mechanics

Exercise:

1. Determine the expectation values for x, x2, p , and p2 of a particle in an infinite rectangular potential well
for the 1st excited state (i.e. n = 2).

2. Calculate the transition energy from the first excited state to the ground state for proton confined to the
nucleus (typical radius of nucleus ≈10-14m). Use the infinite rectangular potential well model.

3. An electron moves with a seed v = 10-3 c inside a 1D box (V = 0) of length 9.7 nm. The potential is infinite
elsewhere. What approximate quantum number does the electron possess. (Ans.: n =8)

4. What is the minimum energy of

(a) A proton

(b) an alpha particle trapped in a 1D region of the size of uranium nucleus (radius ≈7 x 10 -15 m)

6.7. Finite rectangular potential well: (particle in a non-rigid box)

An infinite potential well is an oversimplification of the problem model that is never realized in practice.

𝑉 , 𝑥 ≤ 0; 𝑅𝑒𝑔𝑖𝑜𝑛 𝐼
𝑉(𝑥) = 0, 0 < 𝑥 < 𝐿; 𝑅𝑒𝑔𝑖𝑜𝑛 𝐼𝐼 ………………..6.28
𝑉 , 𝑥 ≥ 𝐿; 𝑅𝑒𝑔𝑖𝑜𝑛 𝐼𝐼𝐼

Fig.: Particle in a finite potential well

The potential energy for a more realistic situation /model of a moving particle/ is a finite rectangular well.

A classical particle with E > V0 can penetrate the gaps at x = 0 and x = L to enter the outer region but with a
diminished speed corresponding to a reduced K.E = E – V0

A classical particle with E < V0 is permanently bound to the region 0 < x < L.

Quantum mechanics asserts, however, that there is some probability that the particle can be found outside 0 <
x < L for V0 > E!

i.e. the wave function Ψ ≠ 0 generally outside the well and so the probability of finding the particle is non-
zero outside the well {i.e p(x < 0 AND x > L) ≠0}.
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Chapter 6: Quantum Mechanics

Determination of Ψ for stationary states (i.e. time independent case).

Case 1: Region I and III (x < 0 & x > L)

Here V = V0 > E and Schrödinger equation becomes:

𝑑 Ψ(x) 2𝑚
+ (𝐸 − 𝑉 )Ψ(x) = 0
𝑑𝑥 ℏ

Letting −𝛾 = (𝐸 − 𝑉 ) ≡ 𝑅𝑒𝑎𝑙 𝑎𝑛𝑑 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒

ℏ

( )
Thus, = 𝛾 Ψ(x)

Giving the solution Ψ(x) = C𝑒 + D𝑒

Since 𝛾 > 0, to keep Ψ(x) finite as x → −∞ and x → +∞

In region I (x < 0), Ψ (x) = C𝑒 (i.e. set D = 0) …… 6.29

In region III (x > L), Ψ (x) = D𝑒 (i.e. set C = 0) …… 6.30

Case 2: Region III (0 ≤x ≤ L)

( )
Here V0 = 0 and = −𝑘 Ψ (x)

where 𝑘 = , giving the solution Ψ (x) = A𝑒 + B𝑒 ….6.31

ℏ

To determine the coefficients C, D, A & B, we apply continuity of the wave function at boundaries and
normalization of Ψ. This can be done only for certain values of E, corresponding to the allowed energies of the
bound particles.

For these energies, the matching conditions specify the entire wave function except for multiplicative
constant, which then is determined from normalization.

Fig. The wave function and its square at boundaries

The fact that Ψ ≠ 0at the walls increases the de Broglie wavelength in the well (compared to that of the
infinite well) and this in turn lowers the energy and momentum of the particle.

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Chapter 6: Quantum Mechanics

The observation can be used to approximate the allowed energies for the bound particle. The wave function
penetrates the exterior region on a scale of length set by a penetration depth δ given by
ℏ
𝛿= = ……6.32
( )

Specifically at a distance 𝛿 beyond the well edge, the wave amplitude has fallen by 1/e of its value at the edge
and approaches to 0 exponentially in the extreme region.

If (by assumption(four) Ψ ≈ 0 beyond 𝛿, the allowed energies of a particle for a finite well would be those for
an infinite well of length 𝐿 + 2𝛿 (provided 𝛿 < 𝐿), i.e.
ℏ
𝐸 ≅ 𝑛 ….. 6.33
( )

where n = 1, 2, 3, …

Since 𝛿 is dependent on E, En must be solved numerically for a given n.

Equation 6.33 is accurate for lowest-dying states and breakdown as 𝐸 → 𝑉 where 𝛿 → ∞.

Thus the number of bound states is limited by 𝑉 (since as 𝐸 → 𝑉 then 𝛿 → ∞.)

A particle with E > V0 is not bound by the well implying the particle may be found in the exterior region with
comparable probability.

Example:

Estimate the ground state energy of an electron confined to a potential well of width L = 0.200 nm and height
V0 of 100 eV.

Solution:

We solve this iteratively

1st iteration

Fig: Problem model

ℏ ℏ . ×
Expecting E >> V0, 𝛿 = ≈ = = 0.0195 𝑛𝑚 < 𝐿
( ) √ × . × × × . ×

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Chapter 6: Quantum Mechanics

Thus, the effective width of the infinite well is 𝐿 = 𝐿 + 2𝛿 = 0.239 nm

The ground state (n= 1) energy of the electron,

𝜋 ℏ 𝜋 × (6.63 × 10 )
𝐸 ≅ 𝑛 = = 6.58 𝑒𝑉
2𝑚(𝐿 + 2𝛿 ) (2𝜋) × 2 × 9.11 × 10 × (0.239 × 10 )

2nd iteration
ℏ . ×
For new decay length, 𝛿 = = = 0.0202 𝑛𝑚
( ) × × . × ×( . )× . ×

3rd iteration

𝐿 = 𝐿 + 2𝛿 = 0.200 + 2 × 0.0202 = 0.240 𝑛𝑚

and

𝜋 ℏ 𝜋 × (6.63 × 10 )
𝐸 ≅ 𝑛 = × 2 = 6.53 𝑒𝑉
2𝑚(𝐿 + 2𝛿 ) (2𝜋) × 2 × 9.11 × 10 × (0.240 × 10 )

The iteration continues until desired accuracy is achieved.

Noting the exact value is E = 6.52 eV, the above iteration is sufficiently accurate!

Exact treatment of energy computation in a finite well

If a particle is in a finite rectangular potential well of height V0 and width L, its energy levels can only be
expressed implicitly (non-closed form) ready only for recursive iteration.

Ψ (x) = C𝑒 , Ψ (x) = D𝑒 and Ψ (x) = A𝑒 + B𝑒

where

( )
 𝛾= = decay constant outside 0 < x < L.
ℏ

 𝑘= = wave number in 0 < x < L.

ℏ

At x = 0, smooth continuity of Ψ(x), i.e.

 Ψ (0) = Ψ (0) giving C = B …. (i)

 Ψ(x) giving γC =kA …. (ii)

Eliminate C by dividing (ii) by (i) giving =

At x = L smooth continuity of Ψ(x), i.e. Ψ (L) = Ψ (L) giving

 𝐴 𝑠𝑖𝑛𝑘𝐿 + 𝐵 𝑐𝑜𝑠𝑘𝐿 = 𝐷𝑒 ….…. (iii)

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Chapter 6: Quantum Mechanics

 Ψ(x) giving 𝑘𝐴𝑐𝑜𝑠𝑘𝐿 − 𝑘𝐵 𝑠𝑖𝑛𝑘𝐿 = −𝛾𝐷𝑒 …. (iv)

Dividing (iv) by (iii) to eliminate B and replacing with , then

𝑘𝐴𝑐𝑜𝑠𝑘𝐿 − 𝑘𝐵 𝑠𝑖𝑛𝑘𝐿
= −𝛾
𝐴 𝑠𝑖𝑛𝑘𝐿 + 𝐵 𝑐𝑜𝑠𝑘𝐿
( )
Or =− or =−
( )

Or 𝑡𝑎𝑛𝑘𝐿 = or 𝑘 = 𝑡𝑎𝑛

and

𝑘 ℏ
𝐸=
2𝑚
For specified values of V0 and L, the last relation can be satisfied only for allowed values of E. (For any other E,
Ψ(x) will not be continuous at x = 0 & x = L.)

Iteration procedure

i. Set V0 and L

ii. Initialize E = 0;

( )
iii. Compute γ0, k0; [From 𝛾 = and 𝑘 = ]
ℏ ℏ

iv. Compute 𝑘 = 𝑡𝑎𝑛

ℏ
v. Compute 𝐸 =

vi. Compute γ1, k1; Go to (iv)

vii. Until 𝐸 − 𝐸 = 10

Exercise:

Use result of above example to verify the ground state energy for an electron confined to a square well of
width 0.200 nm and V0 = 100 eV is about 6.52 eV.

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Chapter 6: Quantum Mechanics

6.8. The harmonic oscillator (quantum oscillator)

Harmonic motion occurs when a system of some kind vibrates about an equilibrium configuration.

The condition for harmonic motion to occur is the presence of a restoring force that acts to return the system
to its equilibrium configuration when it is disturbed; the inertia of the masses involved causes them to
overshoot equilibrium, and the system oscillates indefinitely if no dissipative processes are involved.

Harmonic oscillator of macroscopic example include a spring supported mass, object floatation in a liquid.

Microscopic examples include a diatomic molecule, an atom in a crystal lattice etc.

The problem of special case of a simple harmonic motion of a particle of mass in which it is subject to a linear
restoring force Fr = μx represents an example of a potential well for which exact results can be obtained.

Fig. Harmonic oscillator of a spring-mass system

From 2nd law of motion:

𝐹 = 𝜇𝑥 = 𝑚𝑎

i.e.

𝑑 𝑥
𝑚 = −𝜇𝑥
𝑑𝑡

Or 𝑚 + 𝜇𝑥 = 0

Letting 𝜔 = and solving the d.e. 𝑥(𝑡) = 𝐴𝑐𝑜𝑠(𝜔𝑡 + ∅)

where A = maximum amplitude and 𝜔 = rad/s

The importance of the simple harmonic oscillator in both classical and modern physics lies in the fact that the
restoring forces reduce to Hook’s law for small displacement x.

i.e. all oscillations are simple harmonic in character when their amplitudes are sufficiently small.

The potential energy of a particle subject to Hook’s force is the work done needed to bring the particle from x
= 0 to x = x against such force:

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Chapter 6: Quantum Mechanics

i.e.

𝐸 = 𝑉(𝑥) = − ∫ 𝐹 (𝑥)𝑑𝑥 = ∫ 𝜇𝑥𝑑𝑥 = 𝜇𝑥 …. 6.34

Fig: Energy distribution

If the maximum swing of the particles is ±𝐴, total energy 𝐸 = 𝜇𝐴 , classically E can have any value! (i.e a
continuous energy spectrum)

Three modifications are necessary on the classical picture to be valid for quantum mechanical applications:

i) Only discrete energy spectrum consisting of certain specific values are allowed continuous energy
spectrum is not allowed

ii) The lowest energy should be some definite value E = E0 > 0.

iii) There is a non-zero probability that the particle can “penetrate” the potential well it is in and go
beyond the limits of –A and +A. { P[(-∞,-A) AND (A,∞)]≠0}

Schrödinger’s equation for the harmonic oscillator with 𝑉 = 𝜇𝑥 becomes

𝑑 Ψ(x) 2𝑚
+ (𝐸 − 𝑉)Ψ(x) = 0
𝑑𝑥 ℏ
Or
( )
+ − 𝑥 Ψ(x) = 0 ……… 6.35
ℏ ℏ

Introducing the dimensionless quantity

𝑦 = 𝑥 implying =
ℏ ℏ

ℏ
Thus, + − 𝑦 Ψ=0
ℏ ℏ ℏ

ℏ
𝛼= = = since 𝜔 =
ℏ ℏ ℏ

so that x and E become in appropriate dimensionless units (from m and J)

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Chapter 6: Quantum Mechanics

+ −𝑦 …….. 6.36
ℏ

Let us try a solution of the form:

Ψ(y) = 𝑓(𝑦)𝑒

which satisfies Ψ(y) → 0 as y → ∞ and lim → 𝑓(𝑦) < 𝑒

Then Eqn 6.36 becomes

− 2𝑦 + −1 𝑓 =0 …… 6.37
ℏ

Set − 1 = 2𝑛 to ensure a bounded solution for f(y) and hence Ψ(y).

ℏ

Thus, − 2𝑦 + 2𝑛𝑓(𝑦) = 0 …… 6.38

This is a standard mathematical equation known as Hermite’s equation whose solution are called Hermite’s
polynomials given by

𝑓(𝑦) = 𝐻 (𝑦) = (−1) 𝑒 𝑒 ……. 6.39

where n = 0, 1, 2, 3, …

The eigen functions (wave functions) of the harmonic oscillator, therefore, are

Ψ (𝑦) = 𝐶𝐻 (𝑦)𝑒 …… 6.40

where C is the normalization constant obtained from ∫ Ψ (𝑦)𝑑𝑦 = 1, 𝑛 = 0, 1, 2, … and given by

𝐶= (2 𝑛!) …… 6.41
ℏ

where 𝑓 = ≡ classical frequency of oscillation.

Thus, Ψ (𝑦) = (2 𝑛!) 𝐻 (𝑦)𝑒 …… 6.42

ℏ

From equation 6.37, the allowed (quantized) energy levels of the harmonic oscillation are given by:

− 1 = 2𝑛
ℏ

from which

𝐸 = 𝑛+ ℏ𝜔 = 𝑛 + ℎ𝑓 ….. 6.43

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Chapter 6: Quantum Mechanics

Hermite polynomials and energy levels:

n 𝐻 (𝑦) 𝐸 Ψ (𝑦)

0 1 1
ℏ𝜔 𝐶𝑒
2
1 2y 3
ℏ𝜔 2𝐶𝑦𝑒
2
2 4𝑦 − 2 5
ℏ𝜔 𝐶(4𝑦 − 2)𝑒
2
3 8𝑦 − 12𝑦 7
ℏ𝜔
2
4 16𝑦 − 48𝑦 + 12 9
ℏ𝜔
2
5 32𝑦 − 160𝑦 + 120𝑦 11
ℏ𝜔
2

Fig. Harmonic oscillator energy levels

The harmonic oscillator energy levels are evenly (i.e 𝐸 − 𝐸 = ℏ𝜔 ) spaced, unlike the energy levels of a
particle in a box whose spacing diverges.

𝐸 = ℏ𝜔 ≠ 0 is the minimum value (called zero-point energy) the oscillator can have in equilibrium with its
surrounding as T => 0o K.

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Chapter 6: Quantum Mechanics

Fig. Classical oscillator limits

Though Ψ ≠ 0for |x| >A (i.e. x< -A & x> A) and hence there is probability of particle’s presence there, tails of
Ψ beyond x = ±A decrease in magnitude for increasing n.

Thus, the classical and quantum pictures begin to resemble each other for increasing n.

Examples:

1. Calculate the probability that a quantum oscillator in its ground state will be found outside the range
permitted for a classical oscillator with same energy.

Solution: 𝑃 = 𝑝[(−∞, −𝐴) ∧ (𝐴, ∞)] = ∫ 𝛹 (𝑥)𝑑𝑥 + ∫ 𝛹 (𝑥)𝑑𝑥

where 𝛹 (𝑥) = 𝐶 exp(− ) and 𝐶 = (2 𝑛!) = =

ℏ ℏ ℏ ℏ

Noting the symmetry of 𝛹 (𝑥)

𝑚𝜔 𝑚𝜔𝑥
𝑃=2 𝛹 (𝑥)𝑑𝑥 = 2 exp(− )𝑑𝑥
𝜋ℏ ℏ

ℏ
Changing variables, 𝑧= 𝑥 leads to 𝑑𝑧 = 𝑑𝑥 or 𝑑𝑥 = 𝑑𝑧
ℏ ℏ

Thus, 𝑃 = ∫ exp(−𝑧 )𝑑𝑧

√

From probability studies, 𝑃 = ∫ exp(−𝑧 )𝑑𝑧 = 𝑒𝑟𝑓𝑐(𝑦) = 𝐶𝑜𝑚𝑝𝑙𝑒𝑚𝑛𝑡𝑎𝑟𝑦 𝑒𝑟𝑟𝑜𝑟 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛

√

𝑒𝑟𝑓𝑐(𝑦) is found from tables (as it is difficult to compute such an integral).

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Chapter 6: Quantum Mechanics

Thus from such tables, 𝑃 = ∫ exp(−𝑧 )𝑑𝑧 = 𝑒𝑟𝑓𝑐(1) = 0.157 ≈ 16%

√

Note: 𝐸 = 𝑛 + ℏ𝜔 and 𝐸 = ℏ𝜔 = 𝜇𝐴

ℏ ℏ
from which 𝐴 = = since 𝜔 =

2. Study how the energy quantization of a quantum oscillator applies to

i) A macroscopic system (such as a 0.01kg mass allowed to a spring of k = 0.1 N/m and moving
harmonically)

ii) A microscopic system such as a hydrogen molecule behaving as a harmonic oscillator with k = 510.5 N/m
a reduced mass m’ = 8.37 x 10-28 kg.

Solution:

.
i) Here the angular frequency 𝜔 = = = 3.16 𝑟𝑎𝑑/𝑠
.

The quantum level spacing : ∆𝐸 = 𝐸 −𝐸 = 𝑖+1+ ℏ𝜔 − 𝑖 + ℏ𝜔 = ℏ𝜔

. ×
Thus, ∆𝐸 = ℏ𝜔 = × 3.16 = 2.08 × 10 𝑒𝑉 << Present limits of detection
× . ×

Thus, the oscillator generates continuous energy virtually!

.
ii) 𝜔 = = = 7.81 × 10 𝑟𝑎𝑑/𝑠
.

∆𝐸 = ℏ𝜔 = 0.513 𝑒𝑉 which can be measured easily with current measurement technology. => discrete
behavior. Here, 𝐸 ≠𝐸

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Applied Modern Physics, ECEG 2101: Extractions by Tezazu Bireda, AAU, AAiT, SECE, July 2022