Nanophysics

Dr. Kazi Hanium Maria

Course Code: PHY 171
Course teacher

1
 QUNATUM MECHANICS:

All physical objects exhibit both PARTICLE AND WAVE

like properties. This was the starting point off quantum
mechanics developed independently by Werner
Heisenberg and Erwin Schrodinger.

Particle properties of waves: Einstein relation:

Energy of photon = h (frequency of wave).

Wave properties of particles: de Broglie relation:

wave length = h/(mass times velocity)
Physical object described by a mathematical function called
the wave function.
Experiments measure the Probability of observing the object.
2
A localized wave or wave packet:
A moving particle in quantum theory

Spread in position Spread in momentum

Superposition of waves
of different wavelengths
to make a packet

Narrower the packet , more the spread in momentum

Basis of Uncertainty Principle
3
The classical world is Deterministic:
➢ Knowing the position and velocity of all objects
at a particular time.
➢ Future can be predicted using known laws of
force and Newton's laws of motion.
Quantum World is Probabilistic:
Knowing the position and velocity with certainty at a given
time is impossible.

Only the probability of future state can be predicted using

known laws of force and equations of quantum mechanics.
Tied together
Observer Observed

4
 Before observation, it is impossible to say
whether an object is a wave or a particle or
whether it exists at all !!
Quantum mechanics is a probabilistic theory of nature

Uncertainty relations of Heisenberg allow you to get away with

anything provided you do it fast enough !!

Example: Bank employee withdrawing cash, using it ,but replacing it

before he can be caught ...

Confined physical systems – an atom – can only exist in

certain allowed states .... they are quantized

5
What is QM trying to tell us?
Bohr: In our description of nature, the
purpose is not to disclose the real
essence of the phenomena but only to
track down, so far as possible, relations
between the manifold aspects of our
experience.

Planck’s guiding spirit: Absolute laws in

Nature must be simple and logical.

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 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.

7
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,vy,vz).
8
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 behavior.

Property Behaviour

mass momentum
Particles position  collisions
velocity

Waves wavelength  diffraction

frequency interference 9
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.g. positional, electrostatic PE

E = ½mv2 + V

 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):

• Define: 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)
acceleration

• 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)}.
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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

12
equation
Solution:
position x(t) = Asin(t) ω= k
m
of particle

1 k
frequency  = /2 =
(of oscillation) 2π m

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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1.4 Experimental Evidence for the Breakdown of Classical Mechanics

• By the early 20th century, there were a number of experimental

results and phenomena that could not be explained by classical
mechanics.

a) Black Body Radiation (Planck 1900)

“UV Catastrophe”
Classical Mechanics
Energy 2000 K (Rayleigh-Jeans)
Radiated

1750 K

1250 K
0 2000 4000 6000 /nm 15
 • Why don’t atoms disintegrate in nanoseconds?
– if electron is “orbiting”, it’s accelerating (wiggling)
– wiggling charges emit electromagnetic radiation (energy)
– loss of energy would cause prompt decay of orbit

• Why don’t hot objects emit

more ultraviolet light than
they do?
– classical theory suggested
a “UV catastrophe,”
leading to obviously
nonsensical infinite energy
radiating from hot body
– Max Planck solved this
problem by postulating
light quanta (now often
called the father of
quantum mechanics)
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 Planck’s Quantum Theory
• Planck (1900) proposed that the light energy emitted by the
black body is quantized in units of h ( = frequency of light).

E = nh (n = 1, 2, 3, …)

• High frequency light only emitted if thermal energy kT  h.

• h – a quantum of energy.

• Planck’s constant h ~ 6.62610−34 Js

• If h → 0 we regain classical mechanics.

• Conclusions:
• Energy is quantized (not continuous).
• Energy can only change by well defined amounts.
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b) 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.
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c) Photoelectric Effect (Einstein 1905)

h Photoelectrons ejected with

-
e− kinetic energy:
e Photelectrons
Ek = h - 

Metal surface
work function = 

• 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). 19
 d) 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
20
in energy or frequency units).
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.

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 1.5 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− E = E2 − E1 = h
n2
E2 E2
n1 h
h
p+
E1 E1
Absorption Emission
• Conclusion: Spectroscopy provides direct evidence for quantization of
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energies (electronic, vibrational, rotational etc.) of atoms and molecules.
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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 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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2.1 Waves Behaving as Particles

a) The Photoelectric Effect

Electromagnetic radiation of frequency  can be thought
of as being made up of particles (photons), each with
energy E = h .

This is the basis of Photoelectron Spectroscopy (PES).

b) Spectroscopy
Discrete spectral lines of atoms and molecules
correspond to the absorption or emission of a photon of
energy h , causing the atom/molecule to change
between energy levels: E = h .

Many different types of spectroscopy are possible.

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c) 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

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• 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/

• Energy of photon E = h = hc/  p=h/s

s
i
• Applying the laws of conservation 
of energy and momentum we get:
e−
p=mev
 h 
Δλ = (λ s − λ i ) =  (1 − cos )

 m e c 
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 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 28
diffracted by crystals.
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.

• By analogy with photons, the associated wavelength of the

particle () is given by:
h h
λ= =
p mv
The fact that particles can behave as waves but also as particles,
depending on which experiment you perform on them, is known
as the wave-particle duality.
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Derivation of De Broglie Relationship

In general, a particle of mass 𝑚 and momentum 𝑝 has an energy,

𝐸= 𝑝2 𝑐 2 + 𝑚2 𝑐 4

Note that, if 𝑝 = 0, this reduces to the famous rest-energy

expression, 𝐸 = 𝑚𝑐 2 . However, photons are massless particles
that always have a finite momentum p = mv. In this case, E = pc

Therefore, Plank’s hypothesis, one quantum of electromagnetic

radiation has energy, 𝐸 = ℎ𝛾.
ℎ𝑐
Thus equation the value of this two expression, ℎ𝛾 = = 𝑝𝑐
𝜆
ℎ ℎ
Solving for the wavelength, 𝜆 = =
𝑝 𝑚𝑣
Hence, de Broglie argued that particles can behave as waves and
this relation can apply for particles.

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Problem-1: Calculate the de Broglie wavelength for an electron with a kinetic energy of
1000 eV.

Solution: The mass of an electron is obtained from the given kinetic energy of 1000 eV:

31
Problem-2: Calculate the de Broglie wavelength for a fastball thrown at 100 miles per hour
and weighing 4 ounces. Comment on whether the wave properties of baseballs could be
experimentally observed.

Solution: Following the unit conversions below, a 4 oz baseball has a mass of 0.11 kg. The
velocity of a fastball thrown at 100 miles per hour in m/s is 44.7 m/s.

The de Broglie wavelength of this fast ball is:

Problem:3 If an electron and a proton have the same velocity, which would have the longer
de Broglie wavelength? a. The electron b. The proton c. They would have the same
wavelength

ℎ
Solution: The equation 𝜆 = implies that the de Broglie wavelength of a particle's matter
𝑝
wave is inversely proportional to its momentum (mass times velocity). Therefore the smaller
mass particle will have a smaller momentum and longer wavelength. The electron is the
lightest and will have the longest wavelength 32
Problem-4: Neutrons have no electric charge, so they do not interact with the atomic
electrons. Hence, they are very penetrating (e.g., typically 10 cm in lead). Neutron diffraction
was proposed in 1934, to exploit de Broglie’s hypothesis about the wave nature of matter.
Calculate the momentum and kinetic energy of a neutron whose wavelength is comparable to
atomic spacing (1.8× 10−10 m).

Solution: Rearranging the de Broglie wavelength relationship,

The relationship for kinetic energy is,

The mass of a neutron is 1.6749273× 10−27 kg.

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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:
– 1-D (x)
– 3-D (x,y,z) = (r) = (r,,) (e.g. atoms)
•  may be time dependent – e.g. (x,y,z,t) 34
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.

35
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.

36
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 write 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 )
37
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

38
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
Ptotal (1D ) =  ψ(x ) dx = 1
−

 2    2
Ptotal (3D ) =  ψ(r ) dτ =    ψ(x, y, z ) dxdydz = 1
− − − −

• i.e. the probability that the particle is somewhere in space = 1.

• In this case,  is said to be a normalized wavefunction. 39

How to Normalize the Wavefunction
2
• If  is not normalized, then:  ψ(r ) dτ = A  1

• A corresponding normalized wavefunction (Norm) can be

defined:
ψ Norm (r ) = ψ(r )
1
A

2
such that:  ψ Norm (r ) dτ = 1

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

(sometimes represented by N).
40
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 41
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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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. 43
• 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

44
• Similar uncertainty relationships apply to other pairs of
observables.
e.g. the energy (E) and lifetime () of a state:

E.  

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

– Short-lived excited states ( well-defined, small ) possess
large uncertainty in the state’s energy (large DE).
 Broad peaks in the spectrum.

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

broader energy (therefore wavelength) bandwidths.
(1 fs = 10−15 s, 1 as = 10−18 s)

45
 Heisenberg’s Uncertainty Principle
• The first statement of the uncertainty principle is that it is
impossible to simultaneously describe a particle’s position and
momentum with absolute accuracy.

• The second statement of the uncertainty principle is that it is

impossible to simultaneously describe with absolute
accuracy the energy of a particle and the instant of time the
particle has this energy.

One consequence of the uncertainty principle is that we

cannot, for example, determine the exact position of an
electron.
46
 Problem-1: An electron is confined to the size of a magnesium atom with a 150 pm radius.
What is the minimum uncertainty in its velocity?

Solution: The uncertainty principle,

can be written as,

and substituting Δ𝑝 = 𝑚Δ𝑣 since the mass is not uncertain.

The relevant parameters are.

mass of electron uncertainty in position: 𝑚𝑒 = 𝑚 = = 9.109383 × 10−31 𝑘𝑔
Uncertainity of the position, Δ𝑥 = 150 × 10−12 𝑚

Problem-2: What is the maximum uncertainty of velocity of the electron described in problem-
1?
Solution: There is no limit to the maximum uncertainty, just the minimum uncertainty.
47
Problem-3: The speed of a 1.0 g projectile is known to be within 10−6 m/s.
(a) Calculate the minimum uncertainty in its position.
(b) What is the maximum uncertainty of its position?

Solution: (a)

This negligible for all intents and purpose as expected for any macroscopic
object.

(b) Unlimited (or the size of the universe). The Heisenberg uncertainty principle
does not quantify the maximum uncertainty.

48
Problem-4: Estimate the minimum uncertainty in the speed of an electron

confined to a hydrogen atom within a diameter of 1 × 10−10 𝑚.

Solution: We need to quantify the uncertainty of the electron in position. We can

estimate that as ±5 × 10−10 𝑚.

Hence, substituting the relevant numbers into uncertainity equation and solving

for Δv we get, ∆𝑣 = 1.15 × 106 𝑘𝑚/𝑠

Note that the uncertainty is significantly greater for the electron in a hydrogen

atom than in the magnesium atom as expected since the magnesium atom is

appreciably bigger.

49
 Problems
1. For the following particles (a) an electron with a kinetic energy of 50eV, (b) a proton with a
kinetic energy of 50eV, calculate the de Broglie wavelength of each
2. a. What is the velocity and wavelength of an electron with a voltage increase of 75 V? b. What is
the momentum of an electron with a de Broglie wavelength of 20 nm?
3. Through what potential a proton must initially at rest fall so its de Broglie wavelength is ?
4. Calculate the energy and wavelength associated with a particle that has fallen through a
potential difference of 3.2 V. Take the mass of a 𝛽 particle to be 9.1 × 10−31 𝑘𝑔 .
5. If a proton is going through a potential difference of 3.0V, what is the momentum and
wavelength associated with this proton? (mass of a proton is equal to 1.67 × 10−27 𝑘𝑔)
6. While studying quantum mechanics one day, you wondered what temperature would be
required for the Jumbo Jawbreaker you were about to eat to have a de Broglie wavelength of
1.9 × 10−24 meters? Assuming that the speed of a Jumbo Jawbreaker can be calculated from the
3𝑘 𝑇 1
equation 𝑣𝑛 = ( 𝐵 )2 . You quickly measure the mass of your Jumbo Jawbreaker and found it to
𝑚
be 0.1 𝑘𝑔.
7. What is the uncertainty in an electron's position if the uncertainty in measuring its velocity is
5 𝑚𝑠 −1 .
8. What is the uncertainty in the speed of an electron if we locate it to within 50 pm?
9. If we know the velocity of an electron to within 3.5 × 107 𝑚𝑠 −1 , then what is the uncertainty in its
position?
10. The relationship between energy and time can be seen through the following uncertainty
principle: ∆𝐸∆𝑡 ≥ ℎ. Through this relationship, it can be interpreted that a particle of mass 𝑚 ,
the energy (𝐸 = 𝑚𝑐 2 ) can come from nothing and return to nothing within a time ∆𝑡 ≤ ℎΤ𝑚𝑐 2 . A
real particle is one that lasts for time (∆𝑡) or more; likewise, a particle that lasts for less than time
(∆𝑡) are called virtual particles. For a charged subatomic particle, a pion, the mass is 2.5 ×
10−28 𝑘𝑔. For a pion to be considered a real particle, what is its minimum lifetime?
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THANKS..

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