QUANTUM

MECHANICS
PHY 361
 2

QUANTUM MECHANICS
(PHY 361)

ISAAC KWESI ACQUAH

 3

INTRODUCTION TO
QUANTUM MECHANICS

LECTURE 2
~LAWRENCE BRAGG 4

“God runs electromagnetics on

Monday, Wednesday, and Friday
by the wave theory, and the
devil runs it by quantum theory
on Tuesday, Thursday, and
Saturday”
❑ As if things were not bad enough for FAILURE OF CLASSICAL MECHANICS
classical physics, de Broglie introduced in 5

1923 another powerful new concept that

classical physics could not reconcile: he
postulated that not only does radiation
exhibit particle-like behaviour but,
conversely, material particles themselves
display wave-like behaviour.

❑ This concept was confirmed

experimentally in 1927 by Davisson and
Germer; they showed that interference
patterns. a property of waves, can be
obtained with material particles such as
[Louis Victor Pierre Raymond, 7th Duc de Broglie (1892 -1987)]
electrons.
❑ Although Bohr’s model for the atom produced results that agree Ending the episodes of
well with experimental spectroscopy, it was criticized for lacking the
ingredients of a theory.
patchworks 6

❑ Like the “quantization” scheme introduced by Planck in 1900, the

postulates and assumptions adopted by Bohr in 1913 were quite
arbitrary and did not follow the first principles of a theory.
❑ It was the dissatisfaction with the arbitrary nature of Planck’s idea
and Bohr’s postulates as well as the need to fit them within the
context of a consistent theory that had prompted Heisenberg and
Schrödinger to search for the theoretical foundation underlying
these new ideas. [Werner Karl Heisenberg (1901 -1976)]

❑ By 1925 their efforts paid off: they skilfully welded the various
experimental findings as well as Bohr’s postulates into a refined
theory: quantum mechanics. In addition to providing an accurate
reproduction of the existing experimental data, this theory turned
out to possess an astonishingly reliable prediction power which
enabled it to explore and unravel many uncharted areas of the
microphysical world.
❑ This new theory had put an end to twenty-five years (1900–1925) of
patchwork which was dominated by the ideas of Planck and Bohr
and which later became known as the old quantum theory. [Erwin Rudolf Josef Alexander Schrödinger
(1887 – 1961)]
 PARTICLE ASPECT OF RADIATION
7
❑ According to classical physics, a particle is characterized by an energy 𝐸 and a
momentum 𝑃, whereas a wave is characterized by an amplitude and a wave vector 𝑘
( 𝑘 = 2𝜋/𝛌) that specifies the direction of propagation of the wave. Particles and waves
exhibit entirely different behaviours.

❑ That is, the “particle” and “wave” properties are mutually exclusive.

❑ These rigid concepts of classical physics led to its failure in explaining a number of
microscopic phenomena such as blackbody radiation, the photoelectric effect, and the
Compton effect. As it turned out, these phenomena could only be explained by
abandoning the rigid concepts of classical physics and introducing a new concept: the
particle aspect of radiation.
 BLACKBODY RADIATION
❑ When heated, a solid object glows and emits thermal radiation. As the temperature 8

increases, the object becomes red, then yellow, then white.

❑ The thermal radiation emitted by glowing solid objects consists of a continuous distribution
of frequencies ranging from infrared to ultraviolet.
❑ The continuous pattern of the distribution spectrum is in sharp contrast to the radiation
emitted by heated gases; the radiation emitted by gases has a discrete distribution
spectrum: a few sharp (narrow), colored lines with no light (i.e., darkness) in between
❑ Understanding the continuous character of the radiation emitted by a glowing solid object
constituted one of the major unsolved problems during the second half of the nineteenth
century.

❑ All attempts to explain this phenomenon by means of the available theories of classical
physics (statistical thermodynamics and classical electromagnetic theory) ended up in
miserable failure. This problem consisted in essence of specifying the proper theory of
thermodynamics that describes how energy gets exchanged between radiation and matter
❑ When radiation falls on an object, some of it might be
absorbed and some reflected. An idealized 9
“blackbody” is a material object that absorbs all of
the radiation falling on it, and hence appears as black
under reflection when illuminated from outside.

❑ When an object is heated, it radiates

electromagnetic energy as a result of the thermal
agitation of the electrons in its surface.

❑ The intensity of this radiation depends on its

frequency and on the temperature; the light it emits
ranges over the entire spectrum.
❑ An object in thermal equilibrium with its
surroundings radiates as much energy as it absorbs.
It thus follows that a blackbody is a perfect absorber
as well as a perfect emitter of radiation.
 HISTORY OF BLACKBODY RADIATION
❑ By the mid-1800s, a wealth of experimental data about blackbody 10

radiation was obtained for various objects.

❑ All these results show that, at equilibrium, the radiation emitted has a
well-defined, continuous energy distribution: to each frequency, there
corresponds an energy density which depends neither on the
chemical composition of the object nor on its shape, but only on the
temperature of the cavity’s walls.

❑ The energy density shows a pronounced maximum at a given

frequency, which increases with temperature; that is, the peak of the
radiation spectrum occurs at a frequency that is proportional to the
temperature .
❑ This is the underlying reason behind the change in colour of a heated
object as its temperature increases, notably from red to yellow to
white. It turned out that the explanation of the blackbody spectrum
was not so easy.
EXPERIMENTAL AND THEORETICAL STUDIES OF BLACKBODY RADIATION
11

In 1879 J. Stefan found experimentally that the total intensity (or the total power per
unit surface area) radiated by a glowing object of temperature T is given by:

𝟒
𝑷 = 𝒂𝝈𝑻
Which is known as the Stefan-Boltzmann law, where 𝜎 = 5.67 × 10−8 Wm−2 K −4 is the
Stefan-Boltzmann constant , and a is a coefficient which is less than or equal to 1; in
the case of a blackbody, 𝑎 = 1. Then in 1884 Boltzmann provided a theoretical
derivation for Stefan’s experimental law by combining thermodynamics and Maxwell’s
theory of electromagnetism.
 WIEN’S ENERGY DENSITY DISTRIBUTION
12
Using thermodynamic arguments, Wien took the Stefan–Boltzmann law and in
1894 he extended it to obtain the energy density per unit frequency of the emitted
blackbody radiation:

𝒖 𝒗, 𝑻 = 𝑨𝒗𝟑 𝒆−𝜷𝒗/𝑻

where A and 𝛽; are empirically defined parameters

(they can be adjusted to fit the experimental data).
𝒖 𝒗, 𝑻 has the dimensions of an energy per unit
volume per unit frequency; its SI units are
𝐽𝑚−3 𝐻𝑧 −1 . Although Wien’s formula fits the high-
frequency data remarkably well, it fails badly at low
frequencies.
 RAYLEIGH’S ENERGY DENSITY DISTRIBUTION
13
❑ In his 1900 attempt, Rayleigh focused on understanding the nature of the
electromagnetic radiation inside the cavity. He considered the radiation to consist
of standing waves having a temperature 𝑇 with nodes at the metallic surfaces.

❑ These standing waves, he argued, are equivalent to harmonic oscillators, for they
result from the harmonic oscillations of a large number of electrical charges,
electrons, that are present in the walls of the cavity.

❑ When the cavity is in thermal equilibrium, the electromagnetic energy density

inside the cavity is equal to the energy density of the charged particles in the walls
of the cavity; the average total energy of the radiation leaving the cavity can be
obtained by multiplying the average energy of the oscillators by the number of
modes (standing waves) of the radiation in the frequency interval 𝑣 to 𝑣 + 𝑑𝑣:

𝟖𝝅𝒗𝟐
𝑵 𝒗 = 𝟑
𝒄
 14
Where, 𝑐 = 3.0 × 108 𝑚/𝑠 is the speed of light; the quantity (8𝜋𝑣 2 /𝑐 3 )𝑑𝑣 gives the
number of modes of oscillation per unit volume in the frequency range 𝑣 to 𝑣 + 𝑑𝑣 is
given by:

𝟖𝝅𝒗𝟐
𝒖 𝒗, 𝑻 = 𝑵 𝒗 𝑬 = 𝟑 𝑬
𝒄

Where, 𝑬 is the average energy of the oscillators present on the walls of the
cavity (or of the electromagnetic radiation in that frequency interval); the
temperature dependence of 𝒖 𝒗, 𝑻 is buried in 𝑬 .
 EQUIPARTITION THEOREM OF CLASSICAL THERMODYNAMICS
❑According to the equipartition theorem of classical thermodynamics, all oscillators 15

in the cavity have the same mean energy, irrespective of their frequencies.

❑ To calculate the average energy, 𝑬 of the oscillators present on the walls of the
cavity (or of the electromagnetic radiation in that frequency interval);
Therefore, ∞
‫׬‬0 𝐸𝑒 −𝐸/𝑘𝑇 𝑑𝐸
𝐸 = ∞ −𝐸/𝑘𝑇
‫׬‬0 𝑒 𝑑𝐸
using a variable change;
𝛽 = 1/𝑘𝑇,
∞
𝜕 −𝛽𝐸
𝜕 1 1
𝐸 =− ln(න 𝑒 𝑑𝐸) = − ln = = 𝑘𝑇
𝜕𝛽 0 𝜕𝛽 𝛽 𝛽
∞
‫׬‬0 𝐸𝑒 −𝐸/𝑘𝑇 𝑑𝐸 Where, k is 1.3807 ×
∴ 𝐸 = ∞ −𝐸/𝑘𝑇 = 𝑘𝑇 10−23 𝐽𝐾 −1 and it is known
‫׬‬0 𝑒 𝑑𝐸 as Boltzmann constant.
 ∞
Since, ‫׬‬0 𝐸𝑒 −𝐸/𝑘𝑇 𝑑𝐸
𝐸 = ∞ −𝐸/𝑘𝑇 = 𝑘𝑇
‫׬‬0 𝑒 𝑑𝐸 16

Then, Rayleigh–Jeans formula becomes:

8𝜋𝑣 2
𝑢 𝑣, 𝑇 = 𝑁 𝑣 𝐸 = 3 𝐸
𝑐
8𝜋𝑣 2
𝑢 𝑣, 𝑇 = 𝑁 𝑣 𝐸 = 3 𝑘𝑇
𝑐

❑ Except for low frequencies, this law is in complete disagreement with experimental data: 𝑢 𝑣, 𝑇 as
given by diverges for high values of 𝑣, whereas experimentally it must be finite as shown in the
figure.
8𝜋𝑣 2
❑ Moreover, if we integrate 𝑢 𝑣, 𝑇 = 𝑁 𝑣 𝐸 = over all frequencies, the integral diverges.
𝑘𝑇
𝑐3
This implies that the cavity contains an infinite amount of energy. This result is absurd. Historically,
8𝜋𝑣 2
this was called the ultraviolet catastrophe, for 𝑢 𝑣, 𝑇 = 𝑁 𝑣 𝐸 = 𝑘𝑇 diverges for high
𝑐3
frequencies (i.e., in the ultraviolet range)—a real catastrophical failure of classical physics indeed!
The origin of this failure can be traced to the derivation of the average energy. It was founded on an
erroneous premise: the energy exchange between radiation and matter is continuous; any amount
of energy can be exchanged.
 PLANCK’S ENERGY DENSITY DISTRIBUTION
❑ By devising an ingenious scheme—interpolation between Wien’s rule and the 17

Rayleigh–Jeans rule—Planck succeeded in 1900 in avoiding the ultraviolet

catastrophe and proposed an accurate description of blackbody radiation.

❑ In sharp contrast to Rayleigh’s assumption that a standing wave can exchange any
amount (continuum) of energy with matter, Planck considered that the energy
exchange between radiation and matter must be discrete.

❑ He then postulated that the energy of the radiation (of frequency 𝑣 ) emitted by the
oscillating charges (from the walls of the cavity)
𝑛 =must
0, 1, 2,come only
3, … … … …in…integer multiples
of ℎ 𝑣 : 𝐸 = 𝑛ℎ 𝑣
where ℎ is a universal constant and ℎ 𝑣 is the energy of a “quantum” of radiation ( 𝑣 )
represents the frequency of the oscillating charge in the cavity’s walls as well as the
frequency of the radiation emitted from the walls, because the frequency of the radiation
emitted by an oscillating charged particle is equal to the frequency of oscillation of the
particle itself).
❑ Assuming that the energy of an oscillator is quantized, Planck showed that the
correct thermodynamic relation for the average energy can be obtained by merely 18
∞
‫׬‬0 𝐸𝑒 −𝐸/𝑘𝑇 𝑑𝐸
replacing the integration of 𝐸 = ∞ —that corresponds to an energy
‫׬‬0 𝑒 −𝐸/𝑘𝑇 𝑑𝐸
continuum—by a discrete summation corresponding to the discreteness of the
oscillators’ energies.
σ∞𝑛=0 𝑛ℎ𝑣 𝑒 −𝑛ℎ𝑣/𝑘𝑇
𝐸 =
σ∞𝑛=0 𝑒
−𝑛ℎ𝑣/𝑘𝑇

To derive the above equation, understand that:

1 𝑥
= σ∞
𝑛=0 𝑥 𝑛
and = σ∞
𝑛=0 𝑛𝑥 𝑛
with 𝑥 = 𝑒 −ℎ𝑣/𝑘𝑇
1−𝑥 1−𝑥 2

σ∞
𝑛=0 𝑛ℎ𝑣 𝑒
−𝑛ℎ𝑣/𝑘𝑇 ℎ𝑣
∴ 𝐸 = ∞ −𝑛ℎ𝑣/𝑘𝑇
= −ℎ𝑣/𝑘𝑇
σ𝑛=0 𝑒 𝑒 −1
Then, Rayleigh–Jeans formula becomes:
𝟖𝝅𝒗𝟐 𝒉𝒗
𝒖 𝒗, 𝑻 = 𝑵 𝒗 𝑬 = 𝟑 −𝒉𝒗/𝒌𝑻
𝒄 𝒆 −𝟏
 𝟖𝝅𝒗𝟐 𝒉𝒗
❑ The equation: 𝒖 𝒗, 𝑻 = 𝑵 𝒗 𝑬 = is known as the Planck’s energy
𝒄𝟑 𝒆−𝒉𝒗/𝒌𝑻 −𝟏 19
distribution.

❑It gives an exact fit to the various experimental

radiation distributions, as displayed in the figure.
The numerical value of h obtained by fitting
𝟖𝝅𝒗𝟐 𝒉𝒗
𝒖 𝒗, 𝑻 = 𝑵 𝒗 𝑬 = with the
𝒄𝟑 𝒆−𝒉𝒗/𝒌𝑻 −𝟏
experimental data is ℎ = 6.626 × 10−34 𝐽/𝑠

❑ In terms of energy density per unit wavelength,

Planck’s energy density can be rewritten as:

𝟖𝝅𝒉𝒄 𝟏
ഥ 𝝀 ,𝑻 =
𝒖
𝝀𝟓 𝒆−𝒉𝒄/𝝀𝒌𝑻 − 𝟏
 TEST YOUR UNDERSTANDING 1
20

a) Show that the maximum of the Planck energy density occurs for a wavelength of the
form 𝛌𝑚𝑎𝑥 = 𝑏/𝑇 , where T is the temperature and b is a constant that needs to be
estimated.

b) Use the relation derived in (a) to estimate the surface temperature of a star if the
radiation it emits has a maximum intensity at a wavelength of 446 nm. What is the
intensity radiated by the star?

a) Estimate the wavelength and the intensity of the radiation emitted by a glowing
tungsten filament whose surface temperature is 3300 K
 PHOTOELECTRIC EFFECT
21
❑The photoelectric effect provides a direct confirmation for the energy
quantization of light.

❑In 1887 Hertz discovered the photoelectric effect: electrons were observed to
be ejected from metals when irradiated with light.
❑ When electromagnetic radiation such as light
photons with the right amount of energy falls on a
cold metal surface, electrons are emitted from the
surface.

❑ Right amount of energy means the incident photons

have the right or suitable frequency.

❑ The emission of electrons from a cold metal surface

occurs when photons of suitable frequency fall on it,
is called photoelectric emission or photoelectric
effect.
 CONDITIONS FOR PHOTOELECTRIC EMISSION
22
❑The incident light photons must have a suitable frequency no matter how strong its
intensity may be. In other words, the emission of electrons does not depend on the
intensity of the incident light photons but depends on the frequency.

❑The metal must be cold. If the metal is hot, the ability of heat to remove the
electrons becomes a factor.
FACTS OR CHARACTERISTICS OF PHOTOELECTRIC EFFECT
❑The rate at which electrons are emitted from a cold metal surface depends on the
intensity of the light incident photons. The higher the intensity of the light photons
incident on the metal, the greater the number of electrons emitted and vice versa.

❑Each light photon has energy, 𝐸 = ℎ𝑣. The energy of incidents light photons
therefore depends on its frequency.

❑The kinetic energy of the photoelectrons depends directly on the frequency of the
incident light photon.
 LAWS OF PHOTOELECTRIC EFFECT
23
❑ If the frequency of the incident radiation is smaller than the metal’s threshold
frequency— a frequency that depends on the properties of the metal—no electron
can be emitted regardless of the radiation’s intensity (Philip Lenard, 1902).

❑ No matter how low the intensity of the incident radiation, electrons will be ejected
instantly the moment the frequency of the radiation exceeds the threshold frequency
𝑣0 .

❑ At any frequency above 𝑣0 , the number of electrons ejected increases with the
intensity of the light but does not depend on the light’s frequency.

❑ The kinetic energy of the ejected electrons depends on the frequency but not on the
intensity of the beam; the kinetic energy of the ejected electron increases linearly
with the incident frequency.
 GENERAL EQUATION OF PHOTOELECTRIC EFFECT
❑ Inspired by Planck’s quantization of electromagnetic radiation, Einstein succeeded in 24

1905 in giving a theoretical explanation for the dependence of photoelectric emission

on the frequency of the incident radiation.

❑ He assumed that light is made of corpuscles each carrying an energy ℎ𝑣 , called

photons. When a beam of light of frequency 𝑣 is incident on a metal, each photon
transmits all its energy ℎ𝑣 to an electron near the surface; in the process, the photon
is entirely absorbed by the electron. The electron will thus absorb energy only in
quanta of energy ℎ𝑣, irrespective of the intensity of the incident radiation.

❑ If ℎ𝑣 is larger than the metal’s work function W—the energy required to dislodge the
electron from the metal (every metal has free electrons that move from one atom to
another; the minimum energy required to free the electron from the metal is called
the work function of that metal)—the electron will then be knocked out of the metal.
Hence no electron can be emitted from the metal’s surface unless
ℎ𝑣 > W 𝒉𝒗 = 𝑾 + 𝑲
 THRESHOLD FREQUENCY
25
❑ According to Einstein, when light photons of sufficiently large energy fall on a metal
surface, part of the energy is used to remove electrons from the metal surface and
the remaining energy is given to the photoelectrons as kinetic energy to move away.

❑ If however, the energy of the incident light photons is minimum and only enough to
eject electrons, then there will be no extra energy left for the ejected electrons to
use as kinetic energy. Such incident photons have minimum frequency.

❑ This minimum frequency is known as threshold frequency or cut-off frequency.

From the relation; ℎ𝑣 = 𝑊 + 𝐾 = ℎ𝑣0 + 𝐾
𝑊 = ℎ𝑣0

𝒗𝟎 = 𝑾ൗ𝒉

Where, 𝑣0 is the threshold frequency

 THRESHOLD WAVELENGTH
26
❑ Threshold wavelength is defined as the biggest wavelength of an incident light
photons which can only eject electrons from a cold metal surface.

❑ Threshold wavelength is also called cut-off wavelength and this varies from metal
to metal.

❑ In other words, every metal has a specific threshold wavelength.

From the relation;
𝑣0 = 𝑊ൗℎ But, 𝑐 = 𝑣0 𝛌0

𝑣0 = 𝑐ൗ𝛌 = 𝑊ൗℎ
0

𝒉𝒄
𝝀𝟎 =
𝑾
 WORK FUNCTION, W
❑ Electrons in a metal are strongly held together by a strong intermolecular force or 27

energy. To remove an electron, at least a certain minimum energy must be supply

to overcome the energy holding the electrons.

❑ What this means is that, this minimum energy supplied is just equal in magnitude
to the energy holding the electrons together in the metal.

❑ This energy is called work function of the metal.

❑ Work function varies from metal to metal.

❑ A metal with small work function means electrons can easily be removed from its
surface. On the other hand, a metal with a large work function means that it is
difficult to remove electrons from the metal surface.
𝑾 = 𝑲 − 𝒉𝒗
ℎ𝑣 = 𝑊 + 𝐾 = ℎ𝑣0 + 𝐾
 STOPPING POTENTIAL
28
❑ When photons of sufficiently high frequency fall on a cold metal surface,
electrons are emitted and these have kinetic energy to leave the metal surface. As
these photoelectrons move away from the metal surface, they collide among
themselves and as a result, some lose energy and others gain energy. Those with
maximum kinetic energy are said to be most energetic electrons.

❑ A potential difference can be applied to stop the most energetic photoelectrons

from leaving the metal surface. If the most energetic photoelectrons are stopped,
all other photoelectrons will also stop.

❑ Such a potential difference is known as stopping potential or barrier potential.

❑ It is important to note that stopping potential does not prevent photoelectric

emission but rather prevents photoelectrons from moving away.
 Suppose a photoelectron leaves a metal surface with kinetic energy given
as: 29
1
𝐾 = 𝑚𝑢2
2
Suppose a voltage ‘V’ is applied around the metal, then the photoelectron gains energy
expressed as
𝐸 = 𝑒𝑉 Where, e is the electronic charge.
If the photoelectron is stopped completely from leaving, then this energy of the
applied voltage, opposes the kinetic energy with equal magnitude, i.e:
1
𝑒𝑉 = 𝑚𝑢2
2
According to the Einstein’s photoelectric equation

𝒉𝒗 = 𝑾 + 𝒆𝑽
 TEST YOUR UNDERSTANDING 2
30

When two ultraviolet beams of wavelengths λ1 = 80 nm and λ2 =

110 nm fall on a lead surface, they produce photoelectrons with
maximum energies 11390 eV and 7154 eV, respectively.

(a)Estimate the numerical value of the Planck constant.

(b)Calculate the work function, the cutoff frequency, and the cutoff
wavelength of lead.
 TEST YOUR UNDERSTANDING 3
31

The photoelectric work function of potassium is 2.0 eV. A p.d is applied between the
metal and another one in order just to prevent the collection of electrons when the
potassium surface is illuminated with a radiation of wavelength 300 nm.

a) What is the p.d for this to occur?

b) Calculate also the speed of the photoelectrons.

32