PHY 342: QUANTUM PHYSICS

Prof. K. J. Oyewumi
Physics Department
University of Ilorin

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References
 P. A. Cox, Introduction to Quantum Theory and Atomic
Structure (Oxford Chemistry Primers 37) OUP, Oxford,
1996.
 A.I.M Rae, Quantum Mechanics (4th edition, IOP)*
 Modern Physics by Mgbenu et al.
 Quantum Mechanics by Fayyazuddin & Riazuddin
 Physics of Atoms & Molecules by Bransden & Joachain
 P. W. Atkins and R. S. Friedman, Molecular Quantum
Mechanics (3rd edn.) OUP, Oxford, 1997.

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References
 F. Mandl, Quantum Mechanics
 P.C.W. Davies, Quantum Mechanics
 A.P. French & E.F. Taylor, An Intro. To Quantum
Mechanics
 S. Gasiorowicz, Quantum Mechanics
 Quantum Mechanics by Walter Greiner
 Quantum Mechanics (Schaum’s Series)

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References
 Quantum Mechanics by Alastair, I. M. R.
 Quantum Mechanics by K. T. Hecht
 Quantum Mechanics by A. S. Davydov
 Quantum Mechanics by E. Merzbacher
 Concepts of Modern Physics by Arthur Beiser
 Modern Quantum Mechanics, J.J.Sakurai, Addison -
Wesley.
 Quantum Mechanics, C.Cohen -Tanoudgi, B. Diu and
F. Laloe, John Wiley & Sons. Vol II

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References
 Quantum Mechanics, L. Schiff, McGraw -Hill.

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 This Timeline has much Entropy.

1922: 1925: 1940:

1905: •Neils Bohr
•Heisenberg
developed the
Pauli proves
won Nobel Spin-Statistic
•Albert Einstein wrote Heisenberg Theorem
Prize in
the paper, "On a
Heuristic Viewpoint
physics
Uncertainty
principle 1936:
1932:
Concerning the
Production and 1918:
•Stern-
Gerlach
•Wolfgang
Pauli •Werner
Publishes
paper on 1944:
Transformation of Experiment Wave
developed the Heisenberg •Wolfgang
Light“; proposed the •Max Planck won (Verified the fourth quantum won Nobel Mechanics Pauli won
idea of energy Nobel prize in space Prize in and
number- the Nobel Prize in
quanta dealing with physics quantization physics Schrödinger's
spin number physics
the photoelectric theory) Equation
effect.

1924:
1921: •Louis De Broglie 1929: 1933: 1943:
1900: 1913: published his Louis De
•Won the Nobel doctoral thesis, Broglie won measures the
•Otto Stern
•Otto Stern
receives Nobel
•Max Planck Prize in Physics “Recherches sur la the Nobel magnetic
•Neils Bohr prize in Physics
proposed theory for his discovery théorie des Prize in moment of the
proposed and
about black- quanta”, which Physics for proton
atomic
body radiation structure theory explanation of introduced his hypothesis. •Schrodinger
the law of the theory of electron wins Nobel
photoelectric waves. prize for his
effect. Schrodinger
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Equation
 “Good" physical laws
 generality,simplicity, precision, fit
experimental observations (e.g.
Newtonian Physics)
 New physics supplants old physics
beyond the domain of validity of old
physics (e.g. Special relativity vs.
Newtonian Physics)

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 The limits of physical theories: classical
physics, quantum physics, special
theory of relativity, relativistic quantum
mechanics (QFT), general theory of
relativity, statistical physics
 Quantum gravity

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 Classical physics = physics before 1900 –
thermodynamics, EM, classical mechanics
 modern physics = the physics of the
twentieth century (after 1900)
 This course is about Quantum physics - atomic
and nuclear structure, and
 special theory of relativity – speed approaching
that of light
 failure of classical physics gives rise to modern
physics

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The 'architects' of Modern (Quantum)
Physics

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The 'architects' of Modern (Quantum) Physics
The Solvay Conference of 1927

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 The Solvay Conference of 1927
A. Picard E. Henriot P. Ehrenfest Ed. Hersen Th. De E. E. W. Pauli W. R. H. Fowler L. Brillouin
Donder Schrodinger Verschaffelt Heisenberg

P. Debye M. W. I. H. A. P. A. M. A. H. L. De M. Born N. Bohr

Knudsen Bragg Kramers Dirac Compton Broglie

I. Langmuir M. Planck M. Curie H. A. A. Einstein P. Langevin Ch.E. Guye C. T. R. O. W.

Lorentz Wilson Richardson

Sir W. H. Bragg, H. Deslandres & E. Van Aubel were absent in the Conference

The fifth Solvay International Conference was held in October 1927. The subject
was electrons and photons, focusing on the newly formulated quantum theory. 17 of
the 29 attendees were or became Nobel prize winners (including Marie Curie, who
alone among them won Nobel prizes in two separate scientific disciplines)

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The 'architects' of Modern (Quantum)
Physics

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 Quantum?
Quantum mechanics is the study of processes
which occur at the atomic scale.

The word "quantum" is derived

From Latin to mean BUNDLE.

Therefore, we are studying the motion of

objects that come in small bundles called
quanta. These tiny bundles that we are
referring to are electrons traveling around
the nucleus.

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 “Newton, forgive me..”, Albert
Einstein
At the atomic scale Newtonian
Mechanics cannot seem to
describe the motion of particles. An
electron trajectory between two
points for example IS NOT a perfect
parabolic trajectory as Newton's
Laws predicts. Where Newton's
Laws end Quantum Mechanics
takes over.....IN A
BIG WAY!
One of the most popular concepts
concerning Quantum Mechanics is called ,
“The Photoelectric Effect”. In 1905, Albert
Einstein published this theory for which he
won the Nobel Prize in 1921.

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 Quantum mechanics
Quantum mechanics began in 1900 when the study of light
emitted by heating solids was studied, so we begin by
discussing the nature of light.
 In 1801Thomas Young gave convincing experimental
evidence for the wave nature of light by showing that light
exhibited diffraction and interference when passed through
two adjacent pinholes.
 In 1860 Maxwell developed Maxwell’s equations
predicted that an accelerated electric charge would radiated
energy in the form of electromagnetic waves.
 light is a type of energy and has wave properties

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 Electromagnetic (EM) radiation travels through space as electric
energy and magnetic energy.
 Wavelength  and frequency  are related by:
 x  = c = 3.00 x 108 m/s
 Frequency (or wavelength) determines the type of radiation All
electromagnetic waves travel at speed c= 3.00 × 1010 cm/sec in
vacuum.
 As a wave, we can describe the energy by its wavelength, which
is the distance from the crest of one wave to the crest of the next
wave.
 The wavelength of electromagnetic radiation can range from
miles (radio waves) to inches (microwaves in a microwave oven)
to millionths of an inch (the light we see) to billionths of an inch
(x-rays).

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  The wavelength of light is more commonly stated in
nanometers (nm). One nanometer is one billionth of a
meter.
 Visible light has wavelengths of roughly 400 nm to
roughly 700 nm. This range of wavelengths is called
the visible spectrum.

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 The Wave Nature of Light

c    E  h 
The speed of light is constant
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 The wavelength  of Electromagnetic Spectrum

radio gamma-ray

visible
microwave infrared UV X-ray

2 1 0 -1
4 3 2 1 0 -1
10 106
10 105
10 10
10 10 10 10 10 10

wavelength (nm)
Low High
Energy  (nm) Energy

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 The speed of EM waves
• Observe what happens when a radio wave and a
visible wave move through space (at same speed of c)

Visual 6 Hz

Radio 3 Hz

• The longer the wavelength, the smaller the frequency

has to be to keep c constant
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 The speed of EM waves
Q1 - Which of the following has the higher frequency
1. visible light or UV (choose one)
2. X-rays or radio waves (choose one)

Q2- Which of the following pairs has the longer

wavelength:
1. Infrared or Ultraviolet (choose one)
2. Gamma rays or Radio waves (choose one)

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 Energy and Matter

Size of Matter Particle Property Wave Property

Large – macroscopic Mainly Unobservable

Intermediate – electron Some Some

Small – photon Few Mainly

For matter E = m c2 For waves E = h 

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 Exercises:
1. Photons have a wavelength of 500 nm. (The symbol nm is
defined as a nanometer = 1010 m) What is the energy of
this photon, and what is the type of the electromagnetic
wave in this case?

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Evidence for the Breakdown of Classical Mechanics

Problems remained from classical mechanics that the special

theory of relativity didn’t explain.
Attempts to apply the laws of classical physics to explain the
behavior of matter on the atomic scale were consistently
unsuccessful.

Problems included:
Blackbody radiation (The electromagnetic radiation emitted by a
heated object)

Photoelectric effect (Emission of electrons by an illuminated metal)

Compton effect, etc.

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Need for Quantum Physics
Between 1900 and 1930, another revolution took place in physics.
A new theory called quantum mechanics was successful in
explaining the behaviour of particles of microscopic size.
The first explanation using quantum theory was introduced by Max
Planck. Many other physicists were involved in other subsequent
developments

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 Basics of Quantum Mechanics
- Particle-Wave Duality -
 Waves as particles:

 Max Plank work on black-body radiation, in which he assumed that the molecules of
the cavity walls, described using a simple oscillator model, can only exchange energy
in quantized units.

 1905 Einstein proposed that the energy in an electromagnetic field is not spread out
over a spherical wavefront, but instead is localized in individual clumbs - quanta.
Each quantum of frequency n travels through space with speed of light, carrying a
discrete amount of energy and momentum =photon => used to explain the
photoelectric effect, later to be confirmed by the x-ray experiments of Compton.

 Particles as waves

 Double-slit experiment, in which instead of using a light source, one uses the
electron gun. The electrons are diffracted by the slit and then interfere in the region
between the diaphragm and the detector.

 Aharonov-Bohm effect

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 The idea of duality is
rooted in a debate over
the nature of light and
matter dating back to the
1600s, when competing
theories of light were
proposed by Huygens
and Newton.

Sir Isaac Newton

Christiaan Huygens
1643 1727
Dutch 1629-1695
light consists of particles
light consists of waves

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 Basics of Quantum Mechanics
- Why Quantum Physics? -
 Classical mechanics (Newton's mechanics) and Maxwell's
equations (electromagnetics theory) can explain
MACROSCOPIC phenomena such as motion of billiard balls
or rockets.
 Quantum mechanics is used to explain microscopic
phenomena such as photon-atom scattering and flow of the
electrons in a semiconductor.
 QUANTUM MECHANICS is a collection of postulates based
on a huge number of experimental observations.
 The differences between the classical and quantum mechanics
can be understood by examining both
 The classical point of view
 The quantum point of view

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 Introduction to Quantum Mechanics

Experimental Evidence for the Breakdown of Classical Mechanics
 A) Radiation
 B) Light is made of particles. The need for a quantification
 1) Black-body radiation (1860-1901)
 2) Atomic Spectroscopy (1888-)
 3) Photoelectric Effect (1887-1905)
 C) Wave–particle duality
 1) Compton Effect (1923).
 2) Electron Diffraction Davisson and Germer (1925).
 3) Young's Double Slit Experiment
 D) Louis de Broglie relation for a photon from relativity
 E) A new mathematical tool: Wavefunctions and operators
 F) Measurable physical quantities and associated operators -
Correspondence principle
 G) The Schrödinger Equation (1926)
 H) The Uncertainty principle

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 Blackbody Radiation
• Known since centuries that when a material is heated, it
radiates heat and its color depends on its temperature
• Example: heating elements on a stove:
– Dark red: 550ºC
– Bright red: 700ºC
– Then: orange, yellow and finally white (really hot !)
 The emission spectrum
depends on the material
 Theoretical description:
simplifications necessary
(Blackbody)

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 Blackbody?
• A material is constantly exchanging heat with its
surrounding (to remain at a constant temperature):
– It absorbs and emits radiations
– Problem: it can reflect incoming radiations, which
makes a theoretical description more difficult
(depends on the environment).
 A blackbody is a perfect absorber:
– Incoming radiations is totally absorbed and none is
reflected.
The light emitted by a black body is called black-body
radiation.

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 BLACKBODY RADIATION
 Object that is HOT
(anything > 0 K is
considered “hot”) emits
EM radiation
 For example, an
incandescent lamp is
red HOT because it
emits a lot of EM wave,
especially in the IR
region

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 Thermal radiation
 An ordinary object can emit and absorb
electromagnetic radiation.
 Particles that constitute an object are constantly in
thermal motion
 These particles interact with pervasive EM fields-
energy is constantly exchanged between the object
and the electromagnetic (EM) field
 The interchange is assumed to be an equilibrium
process occurring at a certain temperature

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 Spectral distribution of energy in
radiation depends only on temperature
 The distribution of intensity of the emitted
radiation from a hot body at a given wavelength
depends on the temperature

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 Radiation
Radiation is the process in which energy is transferred by means
of electromagnetic waves.
Heat transfer by radiation can take place through vacuum. This is
because electromagnetic waves are involved in radiation and
they can propagate through empty space.

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 Black Body
The temperature of the lampblack
block rises faster than the silver block
because the black surface absorbs
radiant energy from the sun at a
greater rate.

Since absorption and emission are

balanced, a material that is a good
absorber, like lampblack, is also a
good emitter, and a material that is a
poor absorber, like polished silver, is
also a poor emitter.

A perfect blackbody, being a perfect

4/1/2021 Physicsabsorber, is also a perfect emitter. 40
Department, Unilorin
 Radiance
 In the measurement of the distribution of intensity
of the emitted radiation from a hot body, one
measures dI where dI is the intensity of EM radiation
emitted between  and  +d about a particular
wavelength .
 Intensity = power per unit area, in unit if Watt per m2.
 Radiance R(,T) is defined as per dI = R(,T) d
 R(, T) is the power radiated per unit area (intensity)
per unit wavelength interval at a given wavelength 
and a given temperature T.
 It’s unit could be in Watt per meter square per m or
 W per meter square per nm.
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Total radiated power per unit area
 The total power radiated per unit area (intensity) of
the BB is given by theintegral
I T    R   , T  d
0
 For a blackbody with a total area of A, its total
power emitted at temperature T is
P T   AI T 
 NB: The SI unit for P is Watt, SI unit for I is Watt
per meter square; for A, the SI unit is meter square.

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Introducing idealized black body
 In reality the spectral distribution of intensity of
radiation of a given body could depend on the type of
the surface which may differ in absorption and
radiation efficiency (i.e. frequency-dependent)

 This renders the study of the origin of radiation by

hot bodies case-dependent (which means no good
because the conclusions made based on one body
cannot be applicable to other bodies that have
different surface absorption characteristics)

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Emmissivity, e
 As a strategy to overcome this non-generality, we introduce
an idealized black body which, by definition, absorbs all
radiation incident upon it, regardless of frequency
 Such idealized body is universal and allows one to
disregard the precise nature of whatever is radiating, since
all BB behave identically
 All real surfaces could be approximate to the behavior of a
black body via a parameter EMMISSIVITY e (e=1 means
ideally approximated, 0< e < 1 means poorly approximated)

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 e

ee

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Stefan’s Law (1874)
 P = sAeT4
 P total power output of a BB or power emitted per unit area.
 A total surface area of a BB, s Stefan-Boltzmann constant,
s = 5.670 x 10-8 W / m2 . K4
 Stefan’s law can be written in terms of intensity
 I = P/A = sT4 , f0r a blackbody, where e = 1
 It is observed that, for fixed , R() increases with
increasing T. At each temperature, there is a wavelength
max , for which R(,T) has its maximum value . A BB is
defined as a body with a surface having an absorptivity
equal to unity, that is a body which absorbs all the radiant
energy falling upon it.

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 The Stefan–Boltzmann Law of Radiation (1884)

The rate at which an object emits radiant energy is proportional to

the fourth power of its absolute temperature.
Q
 P  seAT .
4

t
σ is the Stefan-Boltzmann constant: σ = 5.67  10-8 W/m2.K4.

e is called the emissivity: a number between 0 and 1.

For perfect radiators e = 1.

A is the surface area.

T is the temperature of the radiator in Kelvin.

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Black-Body Radiation Laws
I  sT 4

The Stefan-Boltzmann Law

(1884)
Gives the total energy being
emitted at all wavelengths by
the blackbody (which is the
area under the Planck Law
curve).
Explains the growth in the height
of the curve as the temperature
increases. Notice that this
growth is very abrupt.
σ = 5.67 * 10-8 J s-1 m-2 K-4, Known
as the Stefan-Boltzmann
constant.

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 Wien’s Displacement Law
 In 1894 W. Wien looked into the relationship between
the temperature and wavelength
maxT = b = 2.898 x 10-3 m.K (Wien’s displacement law)
 max is the wavelength at which the curve peaks
 T is the absolute temperature
 The wavelength at which the intensity peaks, max, is
inversely proportional to the absolute temperature
 As the temperature increases, the peak wavelength max is
“displaced” to shorter wavelengths.

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Black-Body Radiation Laws
b
max 
T
Wein Displacement Law
- It tells us as we heat an object up, its
color changes from red to orange to
white hot.
- You can use this to calculate the
temperature of stars.
The surface temperature of the Sun is
5778 K, this temperature
corresponds to a peak emission =
502 nm = about 5000 Å.
- b is a constant of proportionality,
called Wien's displacement
constant and equals 2.897 768 5(51)
× 10–3 m K = 2.897768 5(51) × 106 nm
K.

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Number density of EM standing wave
modes in the cavity
 The number of independent standing waves G()d in
the frequency interval between  and +d per unit
volume in the cavity is (by applying statistical
mechanics)
8 2 d
G   d 
c3
 The next step is to find the average energy per
standing wave

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The average energy per standing wave, e
 Theorem of equipartition of energy (a mainstay
theorem from statistical mechanics) says that the
average energy per standing wave is
 e = kT
k  1.38 1023 J/K, Boltzmann constant
 In classical physics, e can take any value
CONTINOUSLY and there is not reason to limit it to
take only discrete values
 (this is because the temperature T is continuous and
not discrete, hence e must also be continuous)

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Energy density in the BB cavity
 Energy density of the radiation inside the BB cavity
in the frequency interval between  and  + d,
= the total energy per unit volume in the cavity in
the frequency interval between  and  + d .

 u (v, T )dv = the number of independent standing

waves in the frequency interval between  and  +
d per unit volume, G()d,  the average energy
per standing wave.
8 2 kTd
 u (v, T )dv = G()d e =
c3

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Energy density in terms of radiance

 The energy density in the cavity in the

frequency interval between  and  + d can be
easily expressed in terms of wavelength,  via c
=  2
8 kTd 8 kT
u  v, T    u ,T   d
c 3
 4

 In experiment we measure the BB in terms of

radiance R(,T) which is related to the energy
density via a factor of c/4:
 R(,T) = (c/4)u(,T )  2 ckT
4
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 Rayleigh-Jeans Law
• Rayleigh-Jeans law for the radiance (based
on classical physics):
2πckT
R  λ ,T  
λ4

• At long wavelengths, the law matched

experimental results fairly well

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 Rayleigh-Jeans Law, cont.
• At short wavelengths,
there was a major
disagreement between
the Rayleigh-Jeans law
and experiment
• This mismatch became

Radiance
known as the ultraviolet
catastrophe or ultraviolet
divergence
• You would have infinite
energy as the wavelength
approaches zero

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 Black-Body Radiation Laws
2ckT
The Rayleigh-Jeans Law. I ( , T ) 
4
* It agrees with experimental
measurements for long
wavelengths.
* It predicts an energy output
that diverges towards infinity
as wavelengths grow smaller.
* The failure has become known
as the ultraviolet catastrophe.

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 Two Catastrophes?
 Classical physics:

 Emission spectrum: a superposition of electromagnetic waves of

different frequencies
 Frequencies allowed: standing waves inside the cavity

 Equipartition of the energy:

 Every standing wave carries kT of energy

 Flaw: when  → 0, the number of standing waves ↑, leading to E → ∞

 [Ultraviolet Catastrophe] Failure of classical theories:

 The work of Rayleigh-Jeans was considered as state-of-the-art, using

well tested theories, which were in very good agreement with
experimental results in many other circumstances.
 Need for a new theory…

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 Max Planck 1858-1947
 Introduced the concept of
“quantum of action”
 Expert in thermodynamics &
statistical mechanics.
 Around 1900: proposes first an
empirical formula (based on real
physics) to reproduce both the
high & low wavelength parts of
the emission spectrum.
 Remarkable agreement with
experimental results.
 In 1918 he was awarded the Nobel
Prize for the discovery of the
quantized nature of energy.
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Planck’s Theory of Blackbody Radiation

 In 1900 Planck developed a theory of blackbody

radiation that leads to an equation for the
intensity of the radiation
 This equation is in complete agreement with
experimental observations

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Planck’s Wavelength Distribution Function

 Planck generated a theoretical expression for the

wavelength distribution (radiance)
2πhc 2
R  λ ,T   5 hc λkT
λ e 1  
 h = 6.626 x 10-34 J.s
 h is a fundamental constant of nature

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Planck’s Wavelength Distribution Function, cont.

 At long wavelengths, Planck’s equation reduces to

the Rayleigh-Jeans expression
 This can be shown by expanding the exponential
term hc 1  hc 
2
hc
ehc λkT
 1     ...  1
λkT 2 !  λkT  λkT
in the long wavelength limit hc  λkT
 At short wavelengths, it predicts an exponential
decrease in intensity with decreasing wavelength
 This is in agreement with experimental results

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Max Planck

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Comparison between Planck’s law of BB radiation
and RJ’s law

2πckT
R  λ ,T  
λ4

correctely fit by
Radiance

Planck's derivation
2
2πhc
R  λ ,T  
λ 5

ehc λkT  1 

4/1/2021 Physics Department, Unilorin 66

Comparison of Rayleigh-Jeans law with Wien's law and Planck's
law, for a body of 8 mK temperature.

http://en.wikipedia.org/wiki/Image:
RWP-comparison.svg

4/1/2021 Physics Department, Unilorin 67

 Rayleigh
Jeans
formula

–Stefan-Boltzman law: R = s T4
–Wien’s displacement law: mT = 2.898£10-3 m¢K
–Rayleigh-Jeans formula: UV Catastrophe
–Planck’s law: quantization ‘h’
4/1/2021 Physics Department, Unilorin 68
How Planck modeled the BB
 He assumed the cavity radiation came from atomic
oscillations in the cavity walls
 Planck made two assumptions about the nature of the
oscillators in the cavity walls

4/1/2021 Physics Department, Unilorin 69

 Planck’s Assumption, 1
 The energy of an oscillator can have only certain discrete
values En
 En = nhƒ
 n =0,1,2,…; n is called the quantum number
 h is Planck’s constant = 6.63 x 10-34 Js
 ƒ is the frequency of oscillation
 the energy of the oscillator is quantized
 Each discrete energy value corresponds to a different
quantum state
 This is in stark contrast to the case of RJ derivation
according to classical theories, in which the energies of
oscillators in the cavity must assume a continuous
distribution
4/1/2021 Physics Department, Unilorin 70
Energy-Level Diagram of the Planck Oscillator
 An energy-level diagram of
the oscillators showing the
quantized energy levels and
allowed transitions
 Energy is on the vertical axis
 Horizontal lines represent the
allowed energy levels of the
oscillators
 The double-headed arrows
indicate allowed transitions

4/1/2021 Physics Department, Unilorin 71

Oscillator in Planck’s theory is quantised in energies (taking
only discrete values)

 The energy of an oscillator can have only certain

discrete values En = nhƒ, n=0,1,2,3,…
 The average energy per standing wave in the Planck
oscillator is

hf
ε  (instead of ε =kT in classical theories)
e hf kT
1

4/1/2021 Physics Department, Unilorin 72

Planck’s Assumption, 2
 The oscillators emit or absorb energy when making a
transition from one quantum state to another
 The entire energy difference between the initial and
final states in the transition is emitted or absorbed as a
single quantum of radiation
 An oscillator emits or absorbs energy only when it
changes quantum states

4/1/2021 Physics Department, Unilorin 73

Pictorial representation of oscillator
transition between states
A quantum of energy hf is
absorbed or emitted during
transition between states
Transition between states

Allowed states of the

oscillators

4/1/2021 Physics Department, Unilorin 74

 Application for Black Body
- The area of Earth's disk as viewed from space
is, Area = πr2.
- The total energy incident on Earth is,
Incident energy = (πr2)So.
- The energy absorbed by the
Earth/atmosphere system, as viewed from
space is
Absorbed energy = (πr2)So(1 - A). As we know
that bodies must be in radiative
equilibrium. The solar energy striking
Earth's disk as viewed from space is re-
emitted as thermal radiation by the surface
of the entire globe, as described by the
Stefan-Boltzmann Law, Emitted energy =
(4πr2)σT4.
- Set the absorbed energy equal to the emitted
energy:
(πr2)So(1 - A) = (4πr2)σTE4, Solving for T yields:
TE = [So(1 - A)/(4σ)](1/4)
= [1370•(1-0.3)/(4•5.67x10-8)](1/4) = 255 K.

4/1/2021 Physics Department, Unilorin 75

 Conclusion
 As the temperature
increases, the peak
wavelength emitted by the
black body decreases.
 As temperature increases,
the total energy emitted
increases, because the total
area under the curve
increases.
 The curve gets infinitely
close to the x-axis but never
touches it.

http://www.astro.ufl.edu/~oliver/ast3722/lectures/BasicDetectors/BlackBody.gif

4/1/2021 Physics Department, Unilorin 76

 To summarise
 Classical BB presents a “ultraviolet catastrophe”
 The spectral energy distribution of electromagnetic radiation in a
black body CANNOT be explained in terms of classical Maxwell EM
theory, in which the average energy in the cavity assumes continuous
values of <e> = kT (this is the result of the wave nature of radiation)
 To solve the BB catastrophe one has to assume that the energy of
individual radiation oscillator in the cavity of a BB is quantised as
per En = nhƒ
 This picture is in conflict with classical physics because in classical
physics energy is in principle a continuous variable that can take any
value between 0 
 One is then lead to the revolutionary concept that ENERGY OF AN
OSCILLATOR IS QUANTISED
 NOTE: Energy is quantized (not continuous).
 Energy can only change by well defined amounts.

4/1/2021 Physics Department, Unilorin 77

 Planck’s Wavelength Distribution Function: A Recap

Planck generated a theoretical expression for the wavelength

distribution. 2πhc 2
I  λ ,T   5 hc λk T
λ e  B

1

 h = 6.626 x 10-34 J.s

 h is a fundamental constant of nature.
At long wavelengths, Planck’s equation reduces to the Rayleigh-Jeans
expression.
At short wavelengths, it predicts an exponential decrease in intensity
with decreasing wavelength.
 This is in agreement with experimental results.

78 Physics Department, Unilorin 4/1/2021

 Assignments

his is in agreement with experimental results.

79 Physics Department, Unilorin 4/1/2021

 Assignments

80 Physics Department, Unilorin 4/1/2021

 Assignments

81 Physics Department, Unilorin 4/1/2021

 "for their discovery of the blackbody form
and anisotropy of the cosmic microwave
background radiation"

George F. Smoot
John C. Mather

4/1/2021 Physics Department, Unilorin 82

 Photoelectric Effect (1887-1905)
discovered by Hertz in 1887 and explained in 1905 by Einstein.

I Albert EINSTEIN
Heinrich HERTZ
(1879-1955)
(1857-1894)

Vacuum
Vide e
e i
e

4/1/2021 Physics Department, Unilorin 83

Photoelectric Effect

The photoelectric effect occurs when light incident on certain metallic surfaces
causes electrons to be emitted from those surfaces.
 The emitted electrons are called photoelectrons.
 They are no different than other electrons.
 The name is given because of their ejection from a metal by light in the
photoelectric effect

84 Physics Department, Unilorin 4/1/2021

 Photoelectric Effect (Einstein 1905)

h Photoelectrons ejected with

-
eelectro kinetic energy:
e Ph
ot ns
Ek = h - F

Metal surface
work function = F

• Ideas of Planck applied to electromagnetic radiation.

• No electrons are ejected (regardless of light intensity) unless 
exceeds a threshold value characteristic of the metal.
• Ek independent of light intensity but linearly dependent on .
• Even if light intensity is low, electrons are ejected if  is above the
threshold. (Number of electrons ejected increases with light
intensity).

• Conclusion: Light consists of discrete packets (quanta) of

energy = photons (Lewis, 1922).
4/1/2021 Physics Department, Unilorin 85
 Basics of Quantum Mechanics
- Photoelectric Effect -
A Photocell is Used to Study the Photoelectric Effect

4/1/2021 Physics Department, Unilorin 86

 - Photoelectric Effect -

Larger light intensity means larger number of photons at a given frequency (Energy)
4/1/2021 Physics Department, Unilorin 87
 - Photoelectric Effect -

Larger frequency, means smaller wavelength, and larger Energy=hf.

4/1/2021 Physics Department, Unilorin 88

What is the Photoelectric Effect?
In very basic terms, it is when electrons are
released from a certain type of metal upon
receiving enough energy from incident light.

So basically, light comes down and strikes the

metal. If the energy of the light wave is
sufficient, the electron will then shoot out of the
metal with some velocity and kinetic energy.

4/1/2021 Physics Department, Unilorin 89

The Electron-Volt = ENERGY

Before we begin to discuss the photoelectric

effect, we must introduce a new type of unit.
Recall:

This is a very useful unit as it shortens our calculations and allows us

to stray away from using exponents.

4/1/2021 Physics Department, Unilorin 90

The Photoelectric Effect
"When light strikes a material, electrons are
emitted. The radiant energy supplies the work
necessary to free the electrons from the
surface."

4/1/2021 Physics Department, Unilorin 91

Photoelectric Fact #1
The LIGHT ENERGY (E) is in the form of quanta
called PHOTONS. Since light is an
electromagnetic wave it has an oscillating
electric field. The more intense the light the
more the field oscillates. In other words, its
frequency is greater.

4/1/2021 Physics Department, Unilorin 92

 c  f
Light Review c  speed of light  constant(vacuum)
c  3x10 8 m / s
c
 f , inverse relationsh ip between  & f

if  , f  and vice versa...

4/1/2021 Physics Department, Unilorin 93

More on Fact #1 E
E  f  E  hf   h
f
c hc
Make sure you USE the correct constant!  f E
 

h hc
6.63x10-34 Js 1.99x10-25 Jm
4.14x10-15 eVs 1.24x103 eVnm

Planck’s Constant is the SLOPE of an

Energy vs. Frequency graph!

4/1/2021 Physics Department, Unilorin 94

Photoelectric Fact #2
The frequency of radiation must be above a certain value
before the energy is enough. This minimum frequency
required by the source of electromagnetic radiation to just
liberate electrons from the metal is known as threshold
frequency, f0.

The threshold frequency

is the X-intercept of the
Energy vs. Frequency
graph!

4/1/2021 Physics Department, Unilorin 95

Photoelectric Fact #3
Work function, f, is defined as the least energy
that must be supplied to remove a free electron
from the surface of the metal, against the
attractive forces of surrounding positive ions.
Shown here is a PHOTOCELL. When
incident light of appropriate frequency
strikes the metal (cathode), the light
supplies energy to the electron. The
energy need to remove the electron
from the surface is the WORK!

Not ALL of the energy goes into work!

As you can see the electron then
MOVES across the GAP to the anode
with a certain speed and kinetic
energy.

4/1/2021 Physics Department, Unilorin 96

Photoelectric Fact #4
The MAXIMUM KINETIC ENERGY is the energy difference between
the MINIMUM AMOUNT of energy needed (ie. the work function)
and the LIGHT ENERGY of the incident photon.
The energy NOT used
Light Energy, E to do work goes into
KINETIC ENERGY as
the electron LEAVES
the surface.

WORK done to
remove the electron

THE BOTTOM LINE: Energy Conservation must still hold true!

4/1/2021 Physics Department, Unilorin 97

Putting it all together
E  hf
K  W  hf
K  hf  W  K  hf  f
y  mx  b
KINETIC ENERGY can be plotted on the y axis and FREQUENCY on the x-
axis. The WORK FUNCTION is the y – intercept as the THRESHOLD
FREQUNECY is the x intercept. PLANCK‘S CONSTANT is the slope of the
graph.

4/1/2021 Physics Department, Unilorin 98

Can we use this idea in a circuit?
We can then use this photoelectric effect idea to
create a circuit using incident light. Of course,
we now realize that the frequency of light must
be of a minimum frequency for this work.

Notice the + and – on the photocell itself. We

recognize this as being a POTENTIAL
DIFFERENCE or Voltage. This difference in
voltage is represented as a GAP that the
electron has to jump so that the circuit works

What is the GAP or POTENTIAL DIFFERENCE is too large?

4/1/2021 Physics Department, Unilorin 99

Photoelectric Fact #5 - Stopping Potential
If the voltage is TOO LARGE the electrons WILL NOT have
enough energy to jump the gap. We call this VOLTAGE point
the STOPPING POTENTIAL.

If the voltage exceeds this value, no photons will be emitted no

matter how intense. Therefore it appears that the voltage has
all the control over whether the photon will be emitted and thus
has kinetic energy.

4/1/2021 Physics Department, Unilorin 100

Wave-Particle Duality
The results of the photoelectric effect allowed
us to look at light completely different.
First we have Thomas Young’s
Diffraction experiment proving that
light behaved as a WAVE due to
constructive and destructive
interference.

Then we have Max Planck who allowed Einstein to build his

photoelectric effect idea around the concept that light is composed of
PARTICLES called quanta.

4/1/2021 Physics Department, Unilorin 101

This led to new questions….
If light is a WAVE and is ALSO a particle, does
that mean ALL MATTER behave as waves?
That was the question that Louis de Broglie
pondered. He used Einstein's famous equation to
answer this question.

4/1/2021 Physics Department, Unilorin 102

YOU are a matter WAVE!
Basically all matter could be said to
have a momentum as it moves.
The momentum however is
inversely proportional to the
wavelength. So since your
momentum would be large
normally, your wavelength would
be too small to measure for any
practical purposes.

An electron, however, due to it’s

mass, would have a very small
momentum relative to a person
and thus a large enough
wavelength to measure thus
producing measurable results.

This led us to start using the Electron

Microscopes rather than traditional
Light microscopes.

4/1/2021 Physics Department, Unilorin 103

 - Photoelectric Effect -

– The photoelectric effect provides evidence for

the particle nature of light.
– It also provides evidence for quantization.
– If light shines on the surface of a metal, there is
a point at which electrons are ejected from the
metal.
– The electrons will only be ejected once the
threshold frequency is reached .
– Below the threshold frequency, no electrons are
ejected.
– Above the threshold frequency, the number of
electrons ejected depend on the intensity of the
light.

4/1/2021 Physics Department, Unilorin 104

 Nature of light
Diffraction, Interference phenomena  light has wave nature
Photoelectric, Compton’s effects  light has particle nature
What is the nature of light?
ANSWER:
From a modern viewpoint,
the light has both wave and particle characteristics

That is The Wave-Particle Duality of Light

“… the wave and corpuscular descriptions are only to be

regarded as complementary ways of viewing one and the same
objective process…” (Pauli, physicist)
4/1/2021 Physics Department, Unilorin 105
1. The Wave Property of Electrons
a. Electron diffraction experiment
(Davisson, Germer, Thomson, 1927)
A beam of either X rays (wave) or
electrons (particle) is directed onto a
target which is a gold foil
The scatter of X rays or electrons by
the gold crystal produces a circular
diffraction pattern on a photographic
film
The pattern of the two experiments
are the same

Particle could act like a wave;

both X rays and electrons are
WAVE
4/1/2021 Physics Department, Unilorin 106
 b. Discussion
 Similar diffraction and interference experiments have been
realized with protons, neutrons, and various atoms
(see “Atomic Interferometer”, Xuan Hoi DO, report of practice
of Bachelor degree of Physics, University Paris-North, 1993)
In 1994, it was demonstrated with iodine molecules I2

Wave interference
patterns of atoms

 Small objects like electrons, protons, neutrons, atoms, and

molecules travel as waves - we call these waves “matter waves”
4/1/2021 Physics Department, Unilorin 107
Electron Diffraction, Set-Up

108 Physics Department, Unilorin Section 40.7 4/1/2021

Electron Diffraction, Experiment
Parallel beams of mono-energetic electrons that are incident on a double slit.
The slit widths are small compared to the electron wavelength.
An electron detector is positioned far from the slits at a distance much greater
than the slit separation.

109 Physics Department, Unilorin Section 40.7 4/1/2021

Electron Diffraction, cont.

If the detector collects electrons for a

long enough time, a typical wave
interference pattern is produced.
This is distinct evidence that electrons
are interfering, a wave-like behavior.
The interference pattern becomes
clearer as the number of electrons
reaching the screen increases.

4/1/2021 Physics Department, Unilorin 110

Section 40.7
Electron Diffraction, Equations

A maximum occurs when d sin θ  mλ

 This is the same equation that was used for light.
This shows the dual nature of the electron.
 The electrons are detected as particles at a localized spot at some instant of
time.
 The probability of arrival at that spot is determined by finding the intensity of
two interfering waves.

111 Physics Department, Unilorin Section 40.7 4/1/2021

Electron Diffraction Explained
An electron interacts with both slits simultaneously.
If an attempt is made to determine experimentally which slit the electron goes
through, the act of measuring destroys the interference pattern.
 It is impossible to determine which slit the electron goes through.
In effect, the electron goes through both slits.
 The wave components of the electron are present at both slits at the same
time.

112 Physics Department, Unilorin Section 40.7 4/1/2021

Arthur Holly Compton

1892 – 1962
American physicist
Director of the lab at the University of
Chicago
Discovered the Compton Effect
Shared the Nobel Prize in 1927

113 Physics Department, Unilorin Section 40.3 4/1/2021

The Compton Effect, Introduction

Compton and Debye extended Einstein’s idea of photon momentum.

The two groups of experimenters accumulated evidence of the inadequacy of the
classical wave theory.
The classical wave theory of light failed to explain the scattering of x-rays from
electrons.

114 Physics Department, Unilorin Section 40.3 4/1/2021

Compton Effect, Classical Predictions

According to the classical theory, em waves incident on electrons should:

 Have radiation pressure that should cause the electrons to accelerate
 Set the electrons oscillating
 There should be a range of frequencies for the scattered electrons.

115 Physics Department, Unilorin Section 40.3 4/1/2021

Compton Effect, Observations

Compton’s experiments showed that, at

any given angle, only one frequency of
radiation is observed.

4/1/2021 Physics Department, Unilorin 116

Section 40.3
Compton Effect, Explanation

The results could be explained by treating the photons as point-like particles

having energy hƒ and momentum h ƒ / c.
Assume the energy and momentum of the isolated system of the colliding
photon-electron are conserved.
This scattering phenomena is known as the Compton effect.

117 Physics Department, Unilorin Section 40.3 4/1/2021

Compton Shift Equation

The graphs show the scattered x-rays

for various angles.
The shifted peak, λ’, is caused by the
scattering of free electrons.
h
λ'  λo  1 cos θ 
mec

 This is called the Compton shift

equation.

4/1/2021 Physics Department, Unilorin 118

Section 40.3
Compton Wavelength

The factor h/mec in the equation is called the Compton wavelength of the
electron and is
h
λC   0.002 43 nm
mec
The unshifted wavelength, λo, is caused by x-rays scattered from the electrons
that are tightly bound to the target atoms.

119 Physics Department, Unilorin Section 40.3 4/1/2021

 Compton effect 1923
playing billiards assuming =h/p

h '
h/ '
h 
h/  

2
p /2m
p
Arthur Holly Compton
American
1892-1962

4/1/2021 Physics Department, Unilorin 120

 The Compton Effect (1923)

 Experiment: A monochromatic beam of X-rays (i) =

incident on a graphite block.

 Observation: Some of the X-rays passing through the

block are found to have longer wavelengths (s).

Intensity
s
i 

i s

4/1/2021 Physics Department, Unilorin 121

 Explanation: The scattered X-rays undergo elastic
collisions with electrons in the graphite.
 Momentum (and energy) transferred from X-rays to
electrons.
 Conclusion: Light (electromagnetic radiation) possesses
momentum.
 Momentum of photon p = h/ p=h/s
s
 Energy of photon E = h = hc/  i

 Applying the laws of conservation
of energy and momentum we get: e
p=mev
 h 
Δ λ   λ s  λ i     1  c o s  

 e 
m c
4/1/2021 Physics Department, Unilorin 122
 Davisson and Germer 1925

Clinton Davisson 2d sin = k 

Lester Germer
In 1927
Diffraction is similarly observed using a mono-
energetic electron beam
Bragg law is verified assuming =h/p
4/1/2021 Physics Department, Unilorin 123
 2.2 Particles Behaving as Waves

Electron Diffraction (Davisson and Germer, 1925)

Davisson and Germer showed that
a beam of electrons could be diffracted
from the surface of a nickel crystal.

Diffraction is a wave property – arises

due to interference between scattered
waves.

This forms the basis of electron

diffraction – an analytical technique for
determining the structures of molecules,
solids and surfaces (e.g. LEED).
NB: Other “particles” (e.g. neutrons,
protons, He atoms) can also be
diffracted by crystals.
4/1/2021 Physics Department, Unilorin 124
 Wave-particle Equivalence.
•Compton Effect (1923).
•Electron Diffraction Davisson and Germer (1925)
•Young's Double Slit Experiment

Wave–particle duality

In physics and chemistry, wave–particle duality is the concept that all matter and
energy exhibits both wave-like and particle-like properties. A central concept of
quantum mechanics, duality, addresses the inadequacy of classical concepts like
"particle" and "wave" in fully describing the behavior of small-scale objects. Various
interpretations of quantum mechanics attempt to explain this apparent paradox.

4/1/2021 Physics Department, Unilorin 125

 Thomas Young 1773 – 1829
English, was born into a family of Quakers.
At age 2, he could read.
At 7, he learned Latin, Greek and maths.
At 12, he spoke Hebrew, Persian and could handle
optical instruments.
At 14, he spoke Arabic, French, Italian and Spanish,
and soon the Chaldean Syriac. "…
He is a PhD to 20 years "gentleman, accomplished
flute player and minstrel (troubadour). He is
reported dancing above a rope."
He worked for an insurance company, continuing
research into the structure of the retina,
astigmatism ...
He is the rival Champollion to decipher
hieroglyphics.
He is the first to read the names of Ptolemy and
Cleopatra which led him to propose a first alphabet
4/1/2021 Physics Department,
of hieroglyphic Unilorin (12 characters).
scriptures 126
 Young's Double Slit Experiment

F1

Source

F2

Ecranwith
Mask Plaque
Screen photo
2 slits
4/1/2021 Physics Department, Unilorin 127
 Young's Double Slit Experiment
This is a typical experiment showing the wave nature of light and interferences.

What happens when we decrease the light intensity ?

If radiation = particles, individual photons reach one spot and there will be no interferences
If radiation  particles there will be no spots on the screen

The result is ambiguous

There are spots
The superposition of all the impacts make interferences

4/1/2021 Physics Department, Unilorin 128

 Young's Double Slit Experiment

Assuming a single electron each time

What means interference with itself ?
What is its trajectory?
If it goes through F1, it should ignore the presence of F2

F1

Source

F2

Mask
Ecran Plaque photo
Screen
with 2
slits

4/1/2021 Physics Department, Unilorin 129

 Young's Double Slit Experiment
There is no possibility of knowing through which split the photon went!
If we measure the crossing through F1, we have to place a screen behind.
Then it does not go to the final screen.
We know that it goes through F1 but we do not know where it would go after.
These two questions are not compatible

F1
Two important differences with classical physics:
Source
• measurement is not independent from observer
F2
• trajectories are not defined; h goes through F1
and F2 both! or through them with equal Mask
Ecran Plaque photo
Screen
probabilities! with 2
slits

4/1/2021 Physics Department, Unilorin 130

 Heat Capacities (Einstein, Debye 1905-06)

 Heat capacity – relates rise in energy of a material with its

rise in temperature:
CV = (dU/dT)V

 Classical physics  CV,m = 3R (for all T).

 Experiment  CV,m < 3R (CV as T).
 At low T, heat capacity of solids determined by
vibrations of solid.

 Einstein and Debye adopted Planck’s hypothesis.

 Conclusion: vibrational energy in solids is quantized:

 vibrational frequencies of solids can
only have certain values ()
 vibrational energy can only change
by integer multiples of h.

4/1/2021 Physics Department, Unilorin 131

 Soon after the
electron discovery in 1887
- J. J. Thomson (1887) Some negative part could
be extracted from the atoms

- Robert Millikan (1910) showed that it was quantified.

-Rutherford (1911) showed that the negative part was diffuse

while the positive part was concentrated.

4/1/2021 Physics Department, Unilorin 132

 Atomic Spectroscopy
Absorption or Emission

Johannes Rydberg 1888

Swedish

n1 → n2 name Converges
to (nm)
1 → ∞ Lyman 91
2 → ∞ Balmer 365
3→ ∞ Pashen 821
4 → ∞ Brackett 1459
5 → ∞ Pfund 2280
6→ ∞ Humphreys 3283
4/1/2021 Physics Department, Unilorin 133
 Atomic Spectroscopy
Absorption or Emission
-R/72
-R/62
-R/52
-R/42
Johannes Rydberg 1888
Swedish
-R/32
IR

-R/22
VISIBLE
Quantum numbers n, levels
are not equally spaced
R = 13.6 eV -R/12
UV
Emission
4/1/2021 Physics Department, Unilorin 134
 Atomic and Molecular Spectroscopy

• It was found that atoms and molecules absorb and emit light only at
specific discrete frequencies  spectral lines (not continuously!).
• e.g. Hydrogen atom emission spectrum (Balmer 1885)

n1 = 1  Lyman
n1 = 2  Balmer
n1 = 3  Paschen
n1 = 4  Brackett
n1 = 5  Pfund ν 1  1 1 
ν    RH  2  2 
c λ n 
 1 n 2 
• Empirical fit to spectral lines (Rydberg-Ritz): n1, n2 (> n1) = integers.
• Rydberg constant RH = 109,737.3 cm-1 (but can also be expressed in
energy or frequency units).
4/1/2021 Physics Department, Unilorin 135
 Revision: Electromagnetic Radiation

A – Amplitude  – wavelength
 - frequency c =  x  or  = c / 

wavenumber  =  / c = 1 / 

c (velocity of light in vacuum) = 2.9979 x 108 m s-1.

4/1/2021 Physics Department, Unilorin 136

 The Bohr Model of the Atom
 The H-atom emission spectrum was rationalized by Bohr
(1913): Energies of H atom are restricted to certain discrete
values (i.e. electron is restricted to well-defined circular
orbits, labelled by quantum number n).
 Energy (light) absorbed in discrete amounts (quanta =
photons), corresponding to differences between these
restricted values: E = E2  E1 = h
e E2
n2 E2
n1 h h
p+
E1 E1
Absorption Emission
• Conclusion: Spectroscopy provides direct evidence for quantization of
energies (electronic, vibrational, rotational etc.) of atoms and molecules.
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 Limitations of Bohr Model & Rydberg-Ritz Equation

• The model only works for hydrogen (and other one electron
ions) – ignores e-e repulsion.

• Does not explain fine structure of spectral lines.

• Note: The Bohr model (assuming circular electron orbits) is

fundamentally incorrect.

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Louis de Broglie

1892 – 1987
French physicist
Originally studied history
Was awarded the Nobel Prize in 1929
for his prediction of the wave nature of
electrons

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Wave Properties of Particles

Louis de Broglie postulated that because photons have both wave and particle
characteristics, perhaps all forms of matter have both properties.
The de Broglie wavelength of a particle is

h h
λ 
p mu

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Frequency of a Particle

In an analogy with photons, de Broglie postulated that a particle would also have
a frequency associated with it
E
ƒ
h
These equations present the dual nature of matter:
 Particle nature, p and E
 Wave nature, λ and ƒ

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Complementarity

The principle of complementarity states that the wave and particle models of
either matter or radiation complement each other.
Neither model can be used exclusively to describe matter or radiation
adequately.

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Davisson-Germer Experiment

If particles have a wave nature, then under the correct conditions, they should
exhibit diffraction effects.
Davisson and Germer measured the wavelength of electrons.
This provided experimental confirmation of the matter waves proposed by de
Broglie.

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Wave Properties of Particles

Mechanical waves have materials that are “waving” and can be described in
terms of physical variables.
 A string may be vibrating.
 Sound waves are produced by molecules of a material vibrating.
 Electromagnetic waves are associated with electric and magnetic fields.
Waves associated with particles cannot be associated with a physical variable.

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Ideal Particle vs. Ideal Wave

An ideal particle has zero size.

 Therefore, it is localized in space.
An ideal wave has a single frequency and is infinitely long.
 Therefore, it is unlocalized in space.
A localized entity can be built from infinitely long waves.

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Particle as a Wave Packet

Multiple waves are superimposed so that one of its crests is at x = 0.

The result is that all the waves add constructively at x = 0.
There is destructive interference at every point except x = 0.
The small region of constructive interference is called a wave packet.
 The wave packet can be identified as a particle.

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Wave Envelope

The dashed line represents the envelope function.

This envelope can travel through space with a different speed than the individual
waves.

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Speeds Associated with Wave Packet

The phase speed of a wave in a wave packet is given by

v phase  ω
k

 This is the rate of advance of a crest on a single wave.

The group speed is given by

v g  dω
dk

 This is the speed of the wave packet itself.

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Speeds, cont.

The group speed can also be expressed in terms of energy and momentum.

dE d  p 2  1
vg       2p   u
dp dp  2m  2m

This indicates that the group speed of the wave packet is identical to the speed of
the particle that it is modeled to represent.

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 de Broglie relation from relativity
Popular expressions of relativity:
m0 is the mass at rest, m in motion

E like to express E(m) as E(p) with p=mv

Ei + T + Erelativistic + ….
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 de Broglie relation from relativity

Application to a photon (m0=0)

To remember

To remember
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 Useful to remember to relate energy
and wavelength

Max Planck

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 1. Classical Mechanics
 Do the electrons in atoms and molecules obey
Newton’s classical laws of motion?

 We shall see that the answer to this question is

“No”.

 This has led to the development of Quantum

Mechanics – we will contrast classical and quantum
mechanics.

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 1.1 Features of Classical Mechanics (CM)

1) CM predicts a precise trajectory for a particle.

velocity v

position r = (x,y,z)

 The exact position (r)and velocity (v) (and hence the

momentum p = mv) of a particle (mass = m) can be known
simultaneously at each point in time.

 Note: position (r),velocity (v) and momentum (p) are

vectors, having magnitude and direction  v = (vx,v y,vz).

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 2) Any type of motion (translation, vibration, rotation) can
have any value of energy associated with it
– i.e. there is a continuum of energy states.

3) Particles and waves are distinguishable phenomena, with

different, characteristic properties and behaviour.

Property Behaviour
mass momentum
Particles position  collisions
velocity
Waves wavelength  diffraction
frequency interference

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 1.2 Revision of Some Relevant Equations in CM

Total energy of particle:

E = Kinetic Energy (KE) + Potential Energy (PE)

T - depends on v V - depends on r

V depends on the system

E = ½mv2 + V
e.g. positional, electrostatic PE
 E = p2/2m + V (p = mv)

Note: strictly E, T, V (and r, v, p) are all defined at a particular

time (t) – E(t) etc..

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  Consider a 1-dimensional system (straight line translational
motion of a particle under the influence of a potential acting
parallel to the direction of motion):

 Definition: position r=x

velocity v = dx/dt
momentum p = mv = m(dx/dt)

PE V
force F = (dV/dx)

 Newton’s 2nd Law of Motion

F = ma = m(dv/dt) = m(d2x/dt2)

 Therefore, if we know the forces acting on a particle we can solve a

differential equation to determine it’s trajectory {x(t),p(t)}.
acceleration

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 1.3 Example – The 1-Dimensional Harmonic Oscillator

x=0
F NB – assuming no friction or
k other forces act on the particle
m (except F).

 The particle experiences a restoring force (F) proportional to its

displacement (x) from its equilibrium position (x=0).

 Hooke’s Law F = kx

k is the stiffness of the spring (or stretching force constant of the bond
if considering molecular vibrations)
k
 Substituting F into Newton’s 2nd Law we get:

m(d2x/dt2) = kx a (second order) differential

equation

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Solution:
position x(t) = Asin(t) ω  k
m

of particle
1 k
frequency  = /2 =
2π m
(of oscillation)
Note: frequency depends only on characteristics of the
system (m,k) – not the amplitude (A)!
x time period  = 1/ 

+A

A

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  Assuming that the potential energy V = 0 at x = 0, it can be shown
that the total energy of the harmonic oscillator is given by:
E = ½kA2

 As the amplitude (A) can take any value, this means that the
energy (E) can also take any value – i.e. energy is continuous.

 At any time (t), the position {x(t)} and velocity {v(t)} can be
determined exactly – i.e. the particle trajectory can be specified
precisely.

 We shall see that these ideas of classical mechanics fail when we go

to the atomic regime (where E and m are very small) – then we
need to consider Quantum Mechanics.

 CM also fails when velocity is very large (as v  c), due to

relativistic effects.

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2. Wave-Particle Duality
 Remember: Classically, particles and waves are
distinct:
 Particles – characterised by position, mass, velocity.
 Waves – characterised by wavelength, frequency.

 By the 1920s, however, it was becoming apparent that

sometimes matter (classically particles) can behave
like waves and radiation (classically waves) can
behave like particles.
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2.3 The De Broglie Relationship (1924)

 In 1924 (i.e. one year before Davisson and Germer’s

experiment), De Broglie predicted that all matter has
wave-like properties.

 A particle, of mass m, travelling at velocity v, has linear

momentum p = mv.
h h
λ 
p mv
 By analogy with photons, the associated wavelength of
the particle () is given by:

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 3. Wavefunctions
 A particle trajectory is a classical concept.
 In Quantum Mechanics, a “particle” (e.g. an electron) does
not follow a definite trajectory {r(t),p(t)}, but rather it is best
described as being distributed through space like a wave.

3.1 Definitions
 Wavefunction () – a wave representing the spatial
distribution of a “particle”.
 e.g. electrons in an atom are described by a wavefunction
centred on the nucleus.
  is a function of the coordinates defining the position of the
classical particle:
 (x)
1-D
 (x,y,z) = (r) = (r,,f) (e.g. atoms)
3-D
  may be time dependent – e.g. (x,y,z,t)
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 The Importance of 
  completely defines the system (e.g. electron in an
atom or molecule).
 If  is known, we can determine any observable
property (e.g. energy, vibrational frequencies, …) of
the system.
 QM provides the tools to determine 
computationally, to interpret  and to use  to
determine properties of the system.

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 3.2 Interpretation of the Wavefunction
 In QM, a “particle” is distributed in space like a wave.
 We cannot define a position for the particle.
 Instead we define a probability of finding the particle at
any point in space.

The Born Interpretation (1926)

“The square of the wavefunction at any point in space is
proportional to the probability of finding the particle
at that point.”

 Note: the wavefunction () itself has no physical meaning.

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1-D System
 If the wavefunction at point x is (x), the probability of
finding the particle in the infinitesimally small region (dx)
between x and x+dx is:

P(x)  (x)2 dx
probability density

 (x) – the magnitude of  at point x.

Why writing 2 instead of 2 ?

 Because  may be imaginary or complex  2 would be
negative or complex.
 BUT: probability must be real and positive (0  P  1).
 For the general case, where  is complex ( = a + ib) then:
2 = * where * is the complex conjugate of .
(* = a – ib) (NB i  ) 1
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3-D System
 If the wavefunction at r = (x,y,z) is (r), the probability of
finding the particle in the infinitesimal volume element
d (= dxdydz) is:

P(r)  (r)2 d

 If (r) is the wavefunction describing

the spatial distribution of an electron
in an atom or molecule, then:
(r)2 = (r) – the electron density at point r

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3.3 Normalization of the Wavefunction

 As mentioned above, probability: P(r)  (r)2 d

 What is the proportionality constant?
 If  is such that the sum of (r)2 at all points in space = 1,
then:
P(x) = (x)2 dx 1-D
P(r) = (r)2 d 3-D

 As summing over an infinite number of infinitesimal steps =

integration, this means:
 2
P to t al 1 D    ψ  x  d x  1


 2    2
P t o t al 3 D    ψ r  d τ     ψ  x, y , z  d xd y d z  1
   
 i.e. the probability that the particle is somewhere in space = 1.
 In this case,  is said to be a normalized wavefunction.
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 How to Normalize the Wavefunction
 If  is not normalized, then: 2

 ψ r  dτ  A  1

 A corresponding normalized wavefunction (Norm)

can be defined:

ψ N o rm r   ψ r 
1
A

2
such that:
 ψ N o rm r  dτ  1

 The factor (1/A) is known as the normalization

constant (sometimes represented by N).
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3.4 Quantization of the
Wavefunction

The Born interpretation of  places restrictions

on the form of the wavefunction:

(a)  must be continuous (no breaks);

(b) The gradient of  (d/dx) must be continuous

(no kinks);

(c)  must have a single value at any point in

space;

(d)  must be finite everywhere;

(e)  cannot be zero everywhere.

• Other restrictions (boundary conditions) depend on the exact system.
• These restrictions on  mean that only certain wavefunctions and  only
certain energies of the system are allowed.

 Quantization of   Quantization of E
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 Basics of Quantum Mechanics
- First Postulate of Quantum Mechanics -

Quantum physicists are interested in all kinds of physical systems

(photons, conduction electrons in metals and semiconductors,
atoms, etc.). State of these rather diverse systems are represented
by the same type of functions  STATE FUNCTIONS.

First postulate of Quantum mechanics:

Every physically-realizable state of the system is described in
quantum mechanics by a state function  that contains all
accessible physical information about the system in that state.

– Physically realizable states  states that can be studied in laboratory

– Accesible information  the information we can extract from the
wavefunction
– State function  function of position, momentum, energy that is
spatially localized.
 Basics of Quantum Mechanics
- First Postulate of Quantum Mechanics -

If 1 and 2 represent two physically-realizable states of the system,

then the linear combination
  c1 1  c 2  2
where c1 and c2 are arbitrary complex constants, represents a third
physically realizable state of the system.

Note:
Wavefunction (x,t)  position and time probability amplitude

Quantum mechanics describes the outcome of an ensemble of

measurements, where an ensemble of measurements consists of a
very large number of identical experiments performed on identical
non-interacting systems, all of which have been identically prepared
so as to be in the same state.
 Basics of Quantum Mechanics
- Second Postulate of Quantum Mechanics -

If a system is in a quantum state represented by a wavefunction ,

then
2
PdV   dV
is the probability that in a position measurement at time t the particle
will be detected in the infinitesimal volume dV.

Note:
2
 ( x, t )  position and time probability density

The importance of normalization follows from the Born interpretation

of the state function as a position probability amplitude. According to
the second postulate of quantum mechanics, the integrated
probability density can be interpreted as a probability that in a
position measurement at time t, we will find the particle anywhere in
space.
 Basics of Quantum Mechanics
- Second Postulate of Quantum Mechanics -

Therefore, the normalization condition for the

wavefunction is:
2 *
 PdV    ( x , y , z ) dV   ( x, y , z ) ( x, y , z ) dV  1

Limitations on the wavefunction:
– Only normalizable functions can represent a quantum
state and these are called physically admissible
functions.
– State function must be continuous and single valued
function.
– State function must be a smoothly-varying function
(continuous derivative).
 Basics of Quantum Mechanics
- Third Postulate of Quantum Mechanics -

Third Postulate:
Every observable in quantum mechanics is represented by an operator which is used to
obtain physical information about the observable from the state function. For an
observable that is represented in classical physics by a function Q(x,p), the corresponding
 
operator is Q( x , p) .
Observable Operator

Position x
Momentum   
p
i x
Energy 
p2  2 2
E  V (x)    V ( x)
2m 2m x 2
 Basics of Quantum Mechanics
- More on Operators -
 An operator is an instruction, a symbol which tells us to perform one or more
mathematical acts on a function, say f(x). The essential point is that they act on a
function.
 Operators act on everything to the right, unless the action is constrained by brackets.
 Addition and subtraction rule for operators:

 
  
Q1  Q2 f ( x)  Q1 f ( x)  Q2 f ( x)
 The product of two operators implies succesive operation:
   

Q1Q2 f ( x)  Q1 Q2 f ( x) 
 The product of two operators is a third operator:
  
Q3  Q1Q2
 Two operators commute if they obey the simple operator expression:
 
 
     
Q1, Q2  Q1Q2  Q2Q1  0  Q1Q2  Q2Q1
 
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Question 1.

Solution:

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Question 2.

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Assignments 1:

Assignments 2:

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Werner Heisenberg

1901 – 1976
German physicist
Developed matrix mechanics
Many contributions include:
 Uncertainty principle
 Received Nobel Prize in 1932

 Prediction of two forms of

molecular hydrogen
 Theoretical models of the nucleus

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Section 40.8
 Uncertainty principle

the Heisenberg uncertainty principle states that

locating a particle in a small region of space
makes the momentum of the particle uncertain;
and conversely, that measuring the momentum of
a particle precisely makes the position uncertain

We already have seen incompatible operators

Werner Heisenberg
German
1901-1976

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It is not surprising to find that quantum mechanics does not predict the position
of an electron exactly. Rather, it provides only a probability as to where the
electron will be found.
We shall illustrate the probability aspect in terms of the system of an electron
confined to motion along a line of length L. Quantum mechanical probabilities
are expressed in terms of a distribution function.
For a plane wave, p is defined and the position is not.
With a superposition of plane waves, we introduce an uncertainty on p and we
localize. Since, the sum of 2 wavefucntions is neither an eigenfunction for p nor
x, we have average values.
With a Gaussian function, the localization below is 1/2

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p and x do not commute and are incompatible
For a plane wave, p is known and x is not (Y*Y=A2 everywhere)
Let’s superpose two waves…
this introduces a delocalization for p and may be localize x

At the origin x=0 and at t=0 we want to increase the total amplitude,
so the two waves Y1 and Y2 are taken in phase
At ± x/2 we want to impose them out of phase
The position is therefore known for x ± x/2
the waves will have wavelengths

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 Superposition of two waves

enveloppe

Y
1

-1
4.95

a (radians)
-2

x/2
0 1 2 3 4 5

x/(2x(√2))
Factor 1/2 a more realistic localization

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 Uncertainty principle
A more accurate calculation localizes more
(1/2 the width of a gaussian) therefore one gets

Werner Heisenberg
German x and p or E and t play symmetric roles
1901-1976 in the plane wave expression;
Therefore, there are two main uncertainty principles

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3.5 Heisenberg’s Uncertainty Principle

“It is impossible to specify simultaneously, with precision, both the momentum

and the position of a particle*”
(*if it is described by Quantum Mechanics)
Heisenberg (1927)

px.x  h / 4 (or /2, where  = h/2).

x – uncertainty in position
px – uncertainty in momentum (in the x-direction)

 If we know the position (x) exactly, we know nothing about momentum (px).
 If we know the momentum (px) exactly, we know nothing about position (x).
 i.e. there is no concept of a particle trajectory {x(t),px(t)} in QM (which applies to
small particles).
 NB – for macroscopic objects, x and px can be very small when compared with x
and px  so one can define a trajectory.
 Much of classical mechanics can be understood in the limit h  0.
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The Uncertainty Principle

In classical mechanics, it is possible, in principle, to make measurements with

arbitrarily small uncertainty.
Quantum theory predicts that it is fundamentally impossible to make
simultaneous measurements of a particle’s position and momentum with infinite
accuracy.
The Heisenberg uncertainty principle states: if a measurement of the position
of a particle is made with uncertainty x and a simultaneous measurement of its
x component of momentum is made with uncertainty px, the product of the two
uncertainties can never be smaller than /2.
xpx 
2

199 Physics Department, Unilorin Section 40.8 4/1/2021

Heisenberg Uncertainty Principle, Explained

It is physically impossible to measure simultaneously the exact position and exact

momentum of a particle.
The inescapable uncertainties do not arise from imperfections in practical
measuring instruments.
The uncertainties arise from the quantum structure of matter.

200 Physics Department, Unilorin Section 40.8 4/1/2021

Heisenberg Uncertainty Principle, Another Form

Another form of the uncertainty principle can be expressed in terms of energy

and time.

E t 
2

This suggests that energy conservation can appear to be violated by an amount

E as long as it is only for a short time interval t.

201 Physics Department, Unilorin Section 40.8 4/1/2021

Uncertainty Principle, final

The Uncertainty Principle cannot be interpreted as meaning that a measurement

interferes with the system.
The Uncertainty Principle is independent of the measurement process.
It is based on the wave nature of matter.

202 Physics Department, Unilorin Section 40.8 4/1/2021

How to Understand the Uncertainty Principle

 To localize a wavefunction () in space (i.e. to specify the

particle’s position accurately, small x) many waves of
different wavelengths () must be superimposed  large px
(p = h/).
2 ~ 1

 The Uncertainty Principle imposes a fundamental (not

experimental) limitation on how precisely we can know (or
determine) various observables.
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  Note – to determine a particle’s position accurately requires
use of short radiation (high momentum) radiation. Photons
colliding with the particle causes a change of momentum
(Compton effect)  uncertainty in p.
 The observer perturbs the system.

 Zero-Point Energy (vibrational energy Evib  0, even at T = 0

K) is also a consequence of the Uncertainty Principle:
 If vibration ceases at T = 0, then position and momentum both
= 0 (violating the UP).

 Note: There is no restriction on the precision in

simultaneously knowing/measuring the position along a
given direction (x) and the momentum along another,
perpendicular direction (z):
 pz.x = 0

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 Similar uncertainty relationships apply to other pairs of
observables.

 e.g. the energy (E) and lifetime () of a state:

E.  

(a) This leads to “lifetime broadening” of spectral lines:

 Short-lived excited states ( well defined, small ) possess
large uncertainty in the energy (large E) of the state.
 Broad peaks in the spectrum.

(b)Shorter laser pulses (e.g. femtosecond, attosecond lasers)

have broader energy (therefore wavelength) band widths.
(1 fs = 1015 s, 1 as = 1018 s)

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 4. Wave Mechanics
 Recall – the wavefunction () contains all the
information we need to know about any particular
system.
 How do we determine  and use it to deduce properties
of the system?
4.1 Operators and Observables
 If  is the wavefunction representing a system, we can
write: Q̂ ψ  Q ψ
where Q – “observable” property of system (e.g. energy,
momentum, dipole moment …) – operator
corresponding to observable Q.

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 More on Operators
 An operator is an instruction, a symbol which tells us to perform one or more
mathematical acts on a function, say f(x). The essential point is that they act on a
function.
 Operators act on everything to the right, unless the action is constrained by brackets.
 Addition and subtraction rule for operators:

 
  
Q1  Q2 f ( x)  Q1 f ( x)  Q2 f ( x)
 The product of two operators implies succesive operation:
   
Q1Q2 f ( x)  Q1 Q2 f ( x) 
 The product of two operators is a third operator:
  
Q3  Q1Q2
 Two operators commute if they obey the simple operator expression:
 
 
     
Q1, Q2  Q1Q2  Q2Q1  0  Q1Q2  Q2Q1
 

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 This is an eigenvalue equation and can be rewritten as:

Q̂  ψ   Q  ψ
operator Q acting on function  multiplied
function  by a number Q
(eigenfunction) (eigenvalue)

(Note:  can’t be cancelled).

Examples: d/dx (eax) = a eax

d2/dx2 (sin ax) = a2 sin ax

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To find  and calculate the properties (observables) of a
system:

1. Construct relevant operator Q̂ ψ  Q ψ

2. Set up equation
3. Solve equation  allowed values of  and Q.
Quantum Mechanical Position and Momentum
Operators
x̂ ψ  x ψ
1. Operator for position in the x-direction is just
 d
multiplied by x px   
ˆ
 i  dx
p̂ x ψ  p x ψ  dψ
  pxψ
i dx
2. Operator for linear momentum in the x-direction:
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 Physics Department, Unilorin 209
Constructing Kinetic and Potential Energy QM Operators
1. Write down classical expression in terms of position and momentum.
2. Introduce QM operators for position and momentum.

Examples
1. Kinetic Energy Operator in 1-D
T̂x
CM px2  QM ˆ
p 2
 2  d2 
Tx  Tˆ x  x
  
2m 2m 2m  dx 2 
 
2. KE Operator in 3-D
CM QM “del-squared”

2 px2  py2  pz2 ˆ

p 2
 2  2  2
 2   2
T 
p
 Tˆ       2
2m 2m  x 2 y 2 z 2  2m
2m 2m  

partial derivatives
operate on (x,y,z)
3. Potential Energy Operator (a function of position)
V̂
 PE operator corresponds to multiplication by V(x), V(x,y,z) etc.
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 Operators associated to physical quantities
We cannot use functions (otherwise we would end with classical mechanics)

Any physical quantity is associated with an operator.

An operator O is “the recipe to transform Y into Y’ ”
We write: O Y = Y’
If O Y = oY (o is a number, meaning that O does not modify Y, just a scaling
factor), we say that Y is an eigenfunction of O and o is the eigenvalue.
We have solved the wave equation O Y = oY by finding simultaneously Y and o
that satisfy the equation.
o is the measure of O for the particle in the state described by Y.

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 Examples of operators in mathematics : P parity

Pf(x) = f(-x)

Even function : no change after x → -x

Odd function : f changes sign after x → -x
y=x2 is even
y=x3 is odd
y= x2 + x3 has no parity: P(x2 + x3) = x2 - x3

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 Examples of operators : A

y is an eigenvector; the eigenvalue is -1

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 Linearity
The operator O is linear if:
O (aY1+ bY1) = O (aY1 ) + O( bY1)

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 Normalization
An eigenfunction remains an eigenfunction
when multiplied by a constant
O(Y)= o(Y) thus it is always possible to
normalize a finite function

Dirac notations <YIY>

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 Mean value

Dirac notations

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 Sum, product and commutation of
(A+B)Y=AY+BY
operators eigenvalues

(AB)Y=ABY wavefunctions

y1=e4x y2=x2 y3=1/x

d/dx 4 -- --

operators x 3 3 3 3

x d/dx -- 2 -1

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 Commutation Relation

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 Other Commutation Relations

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 Sum, product and commutation of operators
[A,C]=AC-CA0

[A,B]=AB-BA=0
[B,C]=BC-CB=0

y1=e4x y2=x2 y3=1/x

A = d/dx 4 -- --

not compatible B = x3 3 3 3
operators
C= x d/dx -- 2 -1
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 Compatibility, incompatibility of operators
[A,C]=AC-CA0
When operators commute, the physical quantities
[A,B]=AB-BA=0 may be simultaneously defined (compatibility)
[B,C]=BC-CB=0
When operators do not commute, the physical
quantities can not be simultaneously defined
(incompatibility)

y1=e4x y2=x2 y3=1/x

compatible
operators A = d/dx 4 -- --

not compatible B = x3 3 3 3
operators
C= x d/dx -- 2 -1
4/1/2021 Physics Department, Unilorin 221
x and d/dx do not commute, are incompatible

Translation and inversion do not commute, are incompatible

Translation
vecteur vector
de translation

Centre d'inversion
Inversion center
A T(A)
I(T(A)) O

I(A) T(I(A)) O A

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4.2 The Schrödinger Equation (1926)
 The central equation in Quantum Mechanics.
 Observable = total energy of system.
 Schrödinger Equation Ĥ ψ  E ψ , where ĤHamiltonian
Operator, E Total Energy and E = T + V.

 SE can be set up for any physical system.

 The form of Hˆ  Tˆ  Vˆ depends on the system.
 Solve SE   and corresponding E.

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 Time-dependent Schrödinger Equation

Without potential E = T
With potential E = T + V

Erwin Rudolf Josef Alexander Schrödinger

Austrian
1887 –1961

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

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

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

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

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

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

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

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

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

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

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Examples

1. Particle Moving in 1-D (x)

2   2ψ 
Hˆ ψ  Tˆ ψ  Vˆ ψ  E ψ  
 x 2
  V  x ψ  E ψ

2m  

 The form of V(x) depends on the physical situation:

 Free particle V(x) = 0 for all x.
 Harmonic oscillator V(x) = ½kx2
2.Particle Moving in 3-D (x,y,z)
2   2ψ  2ψ  2ψ 
      V  x, y , z ψ  E ψ
 SE  2m  x 2 y 2 z 2 
 
2 2
  ψ  V  x, y , z ψ  E ψ Note: The SE is a second order
2m differential equation
or
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 Kinetic energy

Classical quantum operator

In 3D :

Calling the laplacian

Pierre Simon, Marquis de Laplace

(1749 -1827)
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 Chemistry is nothing but an application of Schrödinger Equation (Dirac)

< YI Y> <Y IOI Y >

Dirac notations

Paul Adrien Dirac 1902 – 1984

Dirac’s mother was British and his father was Swiss.

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4.3 Particle in a I-D Box

System
 Particle of mass m in 1-D box of length L.
 Position x = 0L.
 Particle cannot escape from box as PE V(x)=  for x = 0, L
(walls).
 
 PE inside box: V(x)= 0 for 0< x < L.
 2   2 ψ 
  Eψ
PE (V)

2 m  x  2 
1-D Schrödinger Eqn.

(V = 0 inside box). 0
0 x L
4/1/2021 Physics Department, Unilorin 243
 2   2ψ 
    Eψ
2m  x 2 
 
 This is a second order differential equation – with general
solutions of the form:
 = A sin kx + B cos kx
  2ψ 
    k 2  A s in kx  B co s kx    k 2 ψ
 x 2 
 

 SE 

2
2m
  2ψ

 x 2
  2 
    
   k 2 ψ  Eψ
  2m 
   

 k 2 2 (i.e. E depends on k).

E
2m

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Restrictions on 

 In principle Schrödinger Eqn. has an infinite number of

solutions.
 So far we have general solutions:
 any value of {A, B, k}  any value of {,E}.
 BUT – due to the Born interpretation of , only certain
values of  are physically acceptable:
 outside box (x<0, x>L) V =   impossible for particle
to be outside the box
 2 = 0   = 0 outside box.
  must be a continuous function
 Boundary Conditions  = 0 at x = 0
 = 0 at x = L.

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Effect of Boundary Conditions
1. x = 0  = A sin kx + B cos kx = B

0 1
=0 B=0
  = A sin kx for all x

2. x = L  = A sin kL = 0

A=0 ?  sin kL = 0 ? 
(or  = 0 for all x)

sin kL = 0  kL = n n = 1, 2, 3, …
(n  0, or  = 0 for all x)
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Allowed Wavefunctions and Energies

 k is restricted to a discrete set of values: k = n/L

 Allowed wavefunctions: n = A sin(nx/L)

 nx 
ψn  2
s in  
 L 
L
 Normalization: A = (2/L) 
k 2 2 n 2π 2 2
En  
2m 2mL 2
 Allowed energies:
n 2h2
En 
8mL 2

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Quantum Numbers
 There is a discrete energy state (En),
corresponding to a discrete
wavefunction (n), for each integer
value of n.
 Quantization – occurs due to boundary
conditions and requirement for  to be
physically reasonable (Born
interpretation).
 n is a Quantum Number – labels each
allowed state (n) of the system and
determines its energy (En).

 Knowing n, we can calculate n and En.

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Properties of the Wavefunction
 nx 
ψn  s in   2
 Wavefunctions are standing waves:  L 
L

 The first 5 normalized wavefunctions for the particle in

the 1-D box:

 Successive functions possess one more half-wave (

they have a shorter wavelength).

 Nodes in the wavefunction – points at which n = 0

(excluding the ends which are constrained to be zero).

 Number of nodes = (n-1) 1  0; 2  1; 3  2 …

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Curvature of the Wavefunction
 If y = f(x) dy/dx = gradient of y (with respect to x).
d2y/dx2 = curvature of y.
 In QM Kinetic Energy  curvature of 
  2ψ 
T   2  ..... 
 
 Higher curvature  (shorter )  higher KE   x 

 For the particle in the 1-D box (V=0):

  2ψ n  n2
KE E n  Tn   
 x 2  L2
 

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Energies

 En  n2/L2  En as n (more nodes in n)

En as L (shorter box)
n (or L)  curvature of n
 KE  En

E  E
2 node

L
1

L1 L2
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 En  n2  energy levels get further apart as n
n E

9h 2
3 E3 
8mL 2

4h 2
2 E2 
8mL 2

h2
1 E1  h2
0 8mL 2 ZPE 
8mL 2
 Zero-Point Energy (ZPE) – lowest energy of particle in
box: h2
Z PE  E mi n  E 1 
8mL 2
 CMEmin = 0
 QM E = 0 corresponds to  = 0 everywhere
(forbidden).
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  If V(x) = V  0, everywhere in box, all energies are
shifted by V.

V=0 V0
2 2 E2=E2+V
n h
En  2
V E2
8mL
E1=E1+V
V
E1

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 Density Distribution of the Particle in the 1-D Box

 The probability of finding the particle 

between x and x+dx (in the state
represented by n) is:
Pn(x) = n(x)2 dx = (n(x))2 dx (n is real)
 nx  2
P n x   2
s in 
2
d x
 L
 L 

 Note: probability is not uniform

2
 n2 = 0 at walls (x = 0, L) for all n.
 n2 = 0 at nodes (where n = 0).

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4.4 Further Examples
(a) Particle in a 2-D Square or 3-D Cubic Box
 Similar to 1-D case, but   (x,y) or (x,y,z).
 Solutions are now defined by 2 or 3 quantum numbers
e.g. [n,m, En,m]; [n,m,l, En,m,l].
 Wavefunctions can be represented as contour plots in 2-D
(b) Harmonic Oscillator
 Similar to particle in 1-D box, but PE V(x) = ½kx2
(c) Electron in an Atom or Molecule
3-D KE operator
V̂ PE due to electrostatic interactions between electron
and all other electrons and nuclei.
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 PROBLEM 1 In a research laboratory, electrons are
accelerated to speed of 6.0  106 m/s. Nearby, a 1.0  10-9 kg
speck of dust falls through the air at a speed of 0.020m/s.
Calculate the de Broglie wavelength in both case

SOLUTION
 For the electron:
h h 6.625 10 34 J .s
  
p mv 9.11 10 31 kg  6.0 10 6 m / s
  1.2 10 10 m
 For the dust speck:
h h 6.625 10 34 J .s
d    9
pd mvd 1.0  10 kg  6.0  0.020 m / s
d  3.3 10 23 m
DISCUSSION: The de Broglie wavelength of the dust speck is so
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small that we do not observe its wavelike behavior
PROBLEM 2 An electron microscope uses 40-keV electrons.
Find the wavelength of this electron.

SOLUTION

The velocity of this electron:

v  2K / m
2  40  10 3  1.6  10 19
v  1.2  10 8 m / s
9.1  10 31
The wavelength of this electron:
h

mv
6.63  10 34 10 o
 31 8  6.1  10 m  6.1 A
9.1 10  1.2  10
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 3. The Schrödinger’s Equation
a. Wave Function and Probability Density
Matter waves:
A moving particle (electron, photon) with momentum p is described
by a matter wave; its wavelength is   h / p
A matter wave is described by a wave function: Y( x, y, z; t )
(called uppercase psi)

Y( x, y, z; t ) is a complex number(a + ib with i2 = -1, a, b: real numbers)

Y( x, y, z; t ) depends on the space (x, y, z) and on the time (t)
The space and the time can be grouped separately:
Y( x, y, z; t )   ( x, y, z ) e  it
 ( x, y , z ) : space- dependentpart (lower casepsi)
 i t
e : time - dependentpart ( : angular frequency)

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 • The meaning of the wave function:  ( x, y, z )
The function  ( x, y, z ) has no meaning
Only  has a physical meaning. That is:
2

The probability per unit time of detecting a particle in a small

volume centered on a given point in the matter 2wave is
proportional to the value at that point of 


2
greater  it is easier to find the particle

   with  is the complex conjugate of 

2
N.B.:  * *

If we write   a  ib   *  a  ib (a, b: real numbers)

• How can we find the wave equation?
Like sound waves described by Newtonian mechanics, or
electromagnetic waves by Maxwell’s equation,
matter waves are described by an equation called Schrödinger’s
equation (1926)
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 b. The Schrödinger’s equation
For the case of one-dimensional motion,
when a particle with the mass m has a potential energy U(x)
Schrödinger’s equation is
d 2 8 2 m
2  2 [ E  U ( x)]  0
dx h
where E is total mechanical energy (potential energy plus kinetic energy)
Schrödinger’s equation is the basic principle
(we cannot derive it from more basic principles)
EXAMPLE: Waves of a free particle
For a free particle, there is no net force acting on it, so
1 2
U ( x)  0 and E  mv d 2
 8 2
m1 2
2   mv   0
Schrödinger’s equation becomes: dx 2
h 2
2 
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 d 2
 2 p 2
By replacing: mv  p   
2  h    0
dx
1 p
With the de Broglie wavelength: 
2  h
and the wave number: K 

we have the Schrödinger’s equation for free particle:
d 2
 K 2  0
dx 2
This differential equation has the most general solution:

 ( x)  AeiKx  BeiKx (A and B are arbitrary constants)

The time-dependent wave function:
Y( x, t )   ( x) ei t  ( AeiKx  BeiKx ) ei t
Y ( x, t )  Aei( Kx t )  Bei ( Kx t )
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Y ( x, t )  Aei( Kx t )  Bei ( Kx t ) : traveling waves

 Ae i ( Kx t ) : wave traveling in the direction of increasing x

 Bei(kx t ) : wave traveling in the negative direction of x
Probability density:
Assume that the free particle travels only in the positive direction
Relabel the constant A as  0 :  ( x)  0eiKx
The probability density is:
2 iKx 2 2 iKx 2
   0e  ( 0 ) e
Because:
iKx 2
e  (eiKx )(eiKx )*  (eiKx )(e iKx )  e 0  1
we have:
2
  (0 ) 2  const
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 2
What is the meaning of a constant probability?   (0 ) 2  const
2
The plot of   (0 ) 2  const
is a straight line parallel to the x axis:
2

2
0

x
O

The probability density is the same for all values of x

The particle has equal probabilities of being anywhere
along the x axis: all positions are equally likely expected
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PROBLEM 3 An electron is moving along x axis with the speed
of 2×106 m/s (known with a precision of 0.50%).
What is the minimum uncertainty with which we can
simultaneously measure the position of the electron along the x
axis? Given the mass of an electron 9.1×10-31 kg

SOLUTION
From the uncertainty principle: x  p  
if we want to have the minimum uncertainty: x  p  
We evaluate the momentum: p  mv  (9.11031 )  (2.05 106 )
p  9.35 1027 kg.m / s
The uncertainty of the momentum is:
p  0.5% p  0.5 / 100 1.87 1024  9.35 1027 kg.m / s
 6.635  10 34 / 2 8
 x 
p
 
 1. 13  10 m  11nm
9.35  10 27
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PROBLEM 4 In an experiment, an electron is determined to be
within 0.1mm of a particular point. If we try to measure the
electron’s velocity, what will be the minimum uncertainty?

SOLUTION
p 
v  
m mx
6.63  10 34 J .s
v 
9.1 10 31 kg  1.0  10  4 m  2
v  1.2m / s
Observation:
We can predict the velocity of the electron to within 1.2m/s.
Locating the electron at one position affects our ability to know
where it will be at later times
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PROBLEM 5 A grain of sand with the mass of 1.00 mg appears
to be at rest on a smooth surface. We locate its position to within
0.01mm. What velocity limit is implied by our measurement of its
position?

SOLUTION
p 
v  
m mx
6.63  10 34 J .s
v 
1 10 6 kg  1.0  10 5 m  2
v  1.1 10 23 m / s
Observation:
The uncertainty of velocity of the grain is so small that we do not
observe it: The grain of sand may still be considered at rest, as our
experience
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Physics Department, Unilorin 266
PROBLEM 6 An electron is confined within a region of width
1.010- 10 m. (a) Estimate the minimum uncertainty in the
x-component of the electron's momentum.
(b) If the electron has momentum with magnitude equal to the
uncertainty found in part (a), what is its kinetic energy? Express
the result in jou1es and in electron volts.

SOLUTION
(a)

(b)

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 PROBLEM 7 A sodium atom is in one of the states labeled
''Lowest excited levels". It remains in that state for an average
time of 1.610-8 s before it makes a transition back to a ground
state, emitting a photon with wavelength 589.0 nm and energy
2.105 eV. What is the uncertainty in energy of that excited state?
What is the wavelength spread of the corresponding spectrum line?

SOLUTION

The fractional uncertainty of the photon energy is

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5. Particle in a square well
• Consider a particle confined to a region 0  x  a where it can
move freely, but subject to strong force at x = 0 and x = a

U  0 when : 0  x  a  

U   when : x  0 or xa U
1. Solution of the Schrödinger’s equation
Schrödinger’s equation for the
particle in the box: d 2 8 2 m
2  2 E  0
dx h 0 a x
By putting: 8 2 m
K2  2
E Infinitely deep
h potential energy well
d 2
 K 2  0
dx 2
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 d 2
 K 2  0  ( x)  AeiKx  BeiKx
dx 2
What values can take the constants A, B, and the condition
for K ?
• With the boundary condition:  ( x  0)  0
 ( x)  AeiKx  BeiKx  Ae 0  Be0  A  B  0
B  A  ( x)  A(eiKx  eiKx )

• Revision: We have the relations

eix  eix eix  eix
cos x  and: sin x 
2 2i

 ( x)  2iA sin Kx  ( x)  C sin Kx

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 • With the boundary condition:  ( x  a)  0
 ( x)  C sin Ka  0 Ka  n K  n / a
The momentum of the particle is: p  K  n / a

p 2   2 2  2
The possible values of energy: E  2  n
2m  2ma 

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 Bound states
Because n is an integer: n  1; 2; 3;...   2 2 
the energy can only have the discrete values: En   2
 n 2
 2ma 
  2 (h / 2 ) 2  h 2
h2
En   2
 n 2  n 2
En  n2
 2ma  8ma 2 8ma 2 3rd excited E
4
We say that the energy is quantized
these values of energy are called energy levels
n=1 ground state (E1) 2nd excited
E3
n=2 first excited state (E2)
n=3 second excited state (E3)
. 1st excited
. E2
. ground
E1
The integer n is called the quantum number
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energy-level diagram
272
 PROBLEM 8

An electron is confined to a one-dimensional, infinitely deep

potential energy well of width a = 100pm.
1/ What is the least energy (in eV) the electron can have?
2/ Compute the energy level of the first excited state, of the
second excited state. Draw the energy level diagram.

SOLUTION
1/ The least energy corresponds to the least quantum number:
n = 1 for the ground state. Thus:
h2 2 
(6.625  10 34 ) 2
E1   1  12
8ma 2 8  9.1 10 31  (100  10 12 ) 2

18
6 .03  10
E1  6.03 1018 J  19
E1  37.7eV
1.6  10
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 2/ The energy level of the first excited state corresponds to n = 2:
h2
E2  2  2 2  4E1 E2  4  37.7eV E2  150.8eV
8ma
The energy level of the second excited state corresponds to n = 3:
h2
E3   3 2
8ma 2
400
 9E1 2nd excited E
 9 37.7eV 300
3

E3  339 .3eV
200
1st excited E2
Observation: 100
ground E1
The levels are not equidistant
0
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 PROBLEM 9
The wave function of a particle confined to an infinitely deep
potential energy well is  ( x)  C sin Kx
Determine the value of C, knowing that the particle must be
somewhere in all space
SOLUTION
2
If the probability density is  (x)
2
The probability of finding the particle in width dx is  ( x) dx
The probability of finding the particle in all space is

  ( x) 2
dx

Because we are sure to find the particle somewhere in all space, the

probability equals the unit:
Normalization condition:
 2
 ( x) dx  1

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For a particle confined to an infinitely deep potential energy well:
 a Ka
  ( x) dx   C sin( Kx) dx  C K
2 2 1
2
 XdX
sin 2

 0 0

With: cos 2 X  1  2 sin X

2
Ka Ka Ka Ka
 XdX  2  [ 1  cos(2 X )] dX  2  dX  2  (cos 2 X )dX
2 1 1 1
sin
0 0 0 0
Ka Ka
 dX  2  (cos 2 X )dX  2  sin 2 X  0  2 sin 2Ka  2 sin 2n  0
1 Ka 1 Ka 1 1
2 0 0
 Normalization condition:
  ( x) dx  C K 2  C 2  2
2 2 1 Ka 2 a

   ( x) dx  1 C  2 / a

 ( x)  2 / a sin Kx
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 PROBLEM 10

The wave function of a particle confined to an infinitely deep

potential energy well is  ( x)  2 / a sin Kx
The depth of the well is a = 100 pm
What is the probability density of finding the particle at the distance
x = 50 pm for the value of the quantum number
1/ n = 1 ?
2/ n = 2 ?

SOLUTION
 n 
We have K  n / a  ( x)  2 / a sin x
 a 
2 2  n 
2
The probability density is  ( x)  sin  x
a  a 
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 SOLUTION
2 2
 
1/ For n = 1:  ( x)  0.02 sin  x (x: pm)
100 
0.02
2


x
0 50 pm 100 pm
2 2 

2/ For n = 2:  ( x)  0.02 sin  x  (x: pm)
 50 
0.02
2


x
0
4/1/2021 50 pm 100 pm
Physics Department, Unilorin 278
 6. Tunneling Phenomena
a. The Square Barrier
The square barrier is represented by a potential energy U(x)
 E0  const 0  x  a
U 
0 x  0;x  a
U

E E0

O a x
• For case of classical particles:
If a particle comes from the left with energy E < E0 , it will be
reflected back at x = 0.
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b. Barrier penetration U

E
ikx
Incident ( Ae ) ik 'x
E0 Transmitted (Ce )
Reflected ( Be ikx ) O a
x
(I) (II) (III)
• In quantum mechanics:
The matter waves will have the solution for the region (I):
I ( x)  Aeikx  Beikx

And the solution for the region (III): III ( x )  Ceik ' x

A particle can go through the potential barrier even if its kinetic

energy is less than the height of the barrier: tunneling effect
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 U

E
Incident Transmitted
E0
Reflected
O a x

I  II  III
x
O a

The wave function I: free incident particles

The wave function II: decays exponentially in the forbidden region
The wave function III: transmitted particles

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