Modern Physics

Blackbody radiation
Experience show that the temperature of a hot and a cold object placed close to each other
equalize in vacuum as well. All macroscopic objects in all temperature emit (and absorb)
thermal radiation spontaneously. This radiation consists of electromagnetic waves.
The energy of the electromagnetic waves emitted by a surface, in unit time and in unit area,
depends on the nature of the surface and on its temperature.
The thermal radiation emitted by many ordinary objects can be approximated as blackbody
radiation. A perfectly insulated cavity that is in thermal equilibrium internally contains black-
body radiation and will emit it through a hole made in its wall, provided the hole is small
enough to have negligible effect upon the equilibrium.

The (absolute) blackbody absorbs all energy, and reflects nothing, which is of course an
idealization. A black-body at room temperature appears black, as most of the energy it radiates
is infra-red and cannot be perceived by the human eye. Black-body radiation has a
characteristic, continuous frequency spectrum that depends only on the body's temperature.
The spectrum is peaked at a characteristic frequency that shifts to higher frequencies (shorter
wavelengths) with increasing temperature, and at room temperature most of the emission is in
the infrared region of the electromagnetic spectrum.

Wien’s displacement law indicates that the maximum of the energy distribution is
displaced within the radiation spectrum of a blackbody in case of a change in temperature.
λmaxT = b
where b is called Wien's displacement constant, is equal to 2.89×10−3 Km.
The Stefan–Boltzmann law states that the power emitted by the surface of a black body
is directly proportional to the fourth power of its absolute temperature and, of course, its
surface area A:

P = σT A 4

where σ ≈ 5,67·10-8W/(m2K4) is the Stefan–Boltzmann constant.

It was impossible to explain the measured spectral emissivity distribution by the concepts and
laws of classical physics. In 1900 Max Planck theoretically derived a formula, which
accurately described the radiation. In order to do that, he had to suppose that energy of the
electromagnetic field inside the cavity does not exist in a continuous, but only in
quantized form, in other words, the energy could only be a multiple of an elementary unit

E=hf
where h is Planck's constant, h = 6,626 ⋅ 10-34 Js. Planck's quantum hypothesis is a
pioneering work, heralding advent of a new era of modern physics and quantum theory.

Photoelectric effect
Scientists observed that many metals emit electrons when illuminated by ultraviolet light. In
case of alkali metals this effect can be generated by visible light as well. The emitted electrons
are called photoelectrons.

Experimental observations of photoelectric emission:

1. For a particular metal, there exists a certain minimum frequency (so called threshold
frequency f0) of incident radiation below which no photoelectrons are emitted, regardless of
the intensity of light.
2. Above the threshold frequency, the maximum kinetic energy of the emitted photoelectron
depends on the frequency of the incident light and on the material, but is independent of the
intensity of the incident light.
3. The rate at which photoelectrons are ejected is directly proportional to the intensity of the
incident light.
4. The time lag between the incidence of radiation and the emission of a photoelectron is very
small, less than 10-8 second.
The theory of the photoelectric effect must explain the experimental observations of the
emission of electrons from an illuminated metal surface. But these experimental observations
can’t be explained by the wave properties of light. In order to solve this problem 1905, Albert
Einstein developed Planck’s theory. He described light as composed of discrete quanta,
now called photons, rather than continuous waves.
The energy of the photon is directly proportional to its frequency: E=hf, where h is the
Planck constant. Now we can apply the conservation of energy to the ideal process when all of
the incoming energy is transferred to an electron:
1
=
hf Wout + me v 2max
2
Wout is the so called work function, usually denoted by φ. This is the minimum work
(i.e. energy) needed to remove an electron from a solid to a point in the vacuum immediately
outside the solid surface. Its value is characteristic for the metal and can be determined by the
threshold frequency f0 :
=
hf 0 W=
out ϕ
If the light can be considered not only as waves but as particles, one have to determine the
mass and momentum of these particles. If we use the famous Einstein-relation
E= m ⋅ c 2 ,
we obtain for the mass of the photon:
E hf h f h
m=
= 2 = ⋅ =
c 2
c c c c⋅λ
Now the momentum of the photon:
h
p= m⋅c =
λ
Expressed by the wave-number:
 
p = k
h
where  = is the so called reduced Planck's constant
2π
We emphasize that Einstein did not negate that the electromagnetic radiation propagates as
waves. Instead, he proposed that light has a dual nature: it can behave as a wave and as a
collection of particles as well.

Line spectra of atoms

The quantum hypothesis also plays an important role in the understanding of atomic spectra
which were started to be explored more than two centuries ago.

The spectrum emitted by a hot solid (such as the filament of a light bulb) is continuous, all
wavelengths are present.

But if the source is a heated gas or vapour, the spectrum includes only a few colours in the
form of isolated lines. This is called emission line spectrum, and the lines are called
spectral lines. The wavelengths or frequencies of the lines are characteristic of the element
emitting the light.
An absorption line is produced when photons from a hot, broad (continuous) spectrum
source pass through a cold material. The intensity of light, over a very narrow frequency
range, is reduced due to absorption by the material

Spectral lines are highly atom-specific, and can be used to identify the chemical composition
of any medium capable of letting light pass through it (typically gas is used). Several elements
were discovered by spectroscopic means, e.g. helium,

Suggested basic level video:

https://www.youtube.com/watch?v=ssFHlRKMRGs

Bohr model of atoms

It was proposed before Bohr that the electron in a hydrogen atom travels around the nucleus in
a circular orbit. However, this violates the principles of classical electrodynamics. The energy
of the electron in an orbit is increasing with its distance from the nucleus. As the electron is
accelerating, it should generate electromagnetic radiation, thereby lose energy, continuously
spiralling into the nucleus. In the reality this does not happen and it was Bohr who explained it
first.

Bohr's postulates

A) Only a limited number of orbits with certain energies are allowed as stationary orbits of
the electron. In other words, the orbits are quantized.
B) For hydrogen, the only orbits that are allowed are those for which the angular
momentum of the electron is an integral multiple of the reduced Planck's constant.
h
Le− = n  , n = 1, 2, 3.... ,  =
2π
The integer number n here is a quantum number describing the stationary state of the
electron.
C) Light is absorbed when an electron jumps to a higher energy orbit and emitted when an
electron falls into a lower energy orbit. The energy of the light emitted or absorbed is
exactly equal to the difference between the energies of the orbits.
 Εi − Εk =
hfik

Apart from his postulates, Bohr applied classical physics, (Newton and Coulomb laws) during
his work. He derived the energy levels in the Hydrogen atom,
1
Εn =
−E*z 2 ⋅
n2
Therefore he managed to deduce the already known frequencies of the emitted light:
Εn − Εm E*  1 1   1 1 
f nm= =  − =
 R  2 − 2 
h h  m2 n2  m n 
where R is the Rydberg-constant.
The predicted and measured Rydberg constant R was in good agreement.
The Bohr model was successful in case of one-electron atoms or ions, such as
• hydrogen
• singly ionized helium He+
• doubly ionized lithium Li++ and so on.
Such atoms are called hydrogen-like atoms.
The most serious problem with the Bohr model is that it does not properly work for multi-
electron atoms, and in the model the atom seems to be a disk, but in the reality it is a sphere.

Wave particle duality of particles, de-Broglie hypothesis

We have already seen the double nature of electromagnetic radiation or light. We concluded
that light can behave like a wave or particle. This was called wave particle duality.
In 1924 de-Broglie suggested the same duality in case of particles like protons or electrons.
He asked the question: If the momentum of a photon can be calculated from its
h
wavelength: p =
λ
then why can’t we reverse this relation to calculate the wavelength of an electron from its
h
momentum: λ=
p
An electron possessing wave properties is subject to constructive and destructive interference.
As will be shown this leads naturally to quantization of electron momentum and kinetic
energy. In order to avoid destructive interference, the wave must be a standing wave, i.e. the
electron's wavefunction must be single-valued, which in this application requires a circular
boundary condition: the wavefunction must match at points separated by one circumference
nλ = 2πr

Using the assumption

h h
λ= =
p mv
we obtain
nh
= 2πr
mv
and therefore the angular momentum is
= = n .
L mvr
It means that de-Broglie derived one of the postulates of Bohr. A few years later, in
1927 Davisson and Germer verified experimentally the existence of matter waves showing
interference of electrons. The obtained wavelength was in good agreement with the de-Broglie
hypothesis.
However, later it turned out that the Bohr model gives an incorrect value L =  for the
ground state (n=1) orbital angular momentum. Instead, L=0 in this case, which cannot be
explained by classical physics.
Although the Bohr model and its underpinning by de-Broglie is not really perfect, the wave–
particle duality, which proposes that every elementary particle exhibits the properties of not
only particles, but also waves, was a key step in the development of quantum mechanics. The
next important steps in this new branch of science was made by Schrödinger and Heisenberg
in 1925 and 1926.

Wave Function
The so called wave function describes the state of the electron (or any physical system).
Usually the Greek letter psi (or sometimes φ) is used, and in general
Ψ ( x, y , z , t ) ,
or in one dimension Ψ(x,t) .
The values of Ψ are usually complex numbers.
Only continuous, bounded functions can describe a real physical system, and usually there is

∫ Ψ dV < C
2
a requirement that the square-integral of Ψ should be bounded:
full
space

What is the physical meaning of the wave function Ψ for a particle?

The wave function describes the distribution of the particle in space. It is related to the
probability of finding the particle in various regions. If we imagine a volume element dV
around a point, the probability that the particle can be found in that volume element is
measured by Ψ dV . The so called probability density is
2

ρ = Ψ ≡ Ψ∗Ψ .
2

The probability of finding a particle in an arbitrary volume is the integral of the probability
density:
p (V) =∫ ρdV =Ψ
∫ dV < 1
2

V V
One can have the information only about where the particle is likely to be, not where it is for
sure.

Principle of superposition: If ψ1 and ψ2 are possible wave-functions of the

system, then the
ψ c1ψ 1 + c2ψ 2
=
linear combination is also a possible wave-function.

We note that in quantum computing, a qubit or quantum bit is a unit of quantum

information—the quantum analogue of the classical binary bit. A qubit is a two-state
quantum-mechanical system. In a classical system, a bit would have to be in one state or the
other. However, quantum mechanics allows the qubit to be in a superposition of both states
at the same time, a property that is fundamental to quantum computing.

Operators
The observables, i.e. those physical quantities which are dynamical variables (i.e. not
constants like m or q) are represented by linear operators, denoted by “hat” on the top of the
 .
letter: O
To obtain specific values for physical quantities, for example energy or momentum, you
operate on the wavefunction with the quantum mechanical operator associated with that
quantity.

In linear algebra, an eigenvector of a square matrix is a vector that points in a direction which
is invariant under the associated linear transformation (eigen here is the German word

meaning self or own). In other words, if v is a nonzero vector, then it is an eigenvector of a
 
square matrix A if Av is a scalar multiple of v . Similarly in case of functions, f is an
eigenfunction of an operator  if the action of that operator is only a multiplication of that
function by a number:

Âf = af
d
where a is a real or complex number. For example, is a linear operator and if
dx
f( x) = eax then
 d ax
e = aeax= a ⋅ f ,
dx
therefore this f is an eigenfunction and the eigenvalue is a.

A number a can be the value of an observable only if a is an eigenvalue of the operator Â

which represents the observable. We have 2 cases:

• The wave function of the system is an eigenfunction of  , i.e. the system is an

eigenstate of the operator. In this case the value of any (precise) measurement of the
physical quantity will be a.
• The wave function of the system is not an eigenfunction of different numbers. For
example the system has the wave function

ψ c1ψ 1 + c2ψ 2
=
which is a combination of eigenstates, i.e.
Âψ 1 = a1ψ 1

Âψ 2 = a2ψ 2 .
Now the result of the measurement can be different numbers. We will measure a1 with
2 2
probability c1 and a2 with probability c2 .

The eigenvalues an may be discrete, and in such cases we can say that the physical variable is
"quantized" and that the index n plays the role of a "quantum number" which characterizes
that state.

Concrete form of the operators

As the first example, there is an x-position operator, which is a simple multiplication:
x̂ = x ⋅ .
It turns the wave function Ψ into xΨ.
Instead of a linear momentum px = mvx there is an x-momentum operator

 ∂
pˆ x =
i ∂x
similarly
 ∂  ∂
=pˆ y = , pˆ z and y = y ⋅ , z = z ⋅ ,
i ∂y i ∂z
The kinetic energy in classical physics:
p2
T = 21 mv 2 = 2m = 1
2m ( p x2 + p y2 + p z2 )
In quantum physics:
T = 21m ( p x p x + p y p y + p z p z ) =

= [ ( ) + ( ) + ( )] =
1  ∂
2 m i ∂x
 ∂
i ∂x
 ∂
i ∂y
 ∂
i ∂y
 ∂
i ∂z
 ∂
i ∂z
1
2m [( ) ( + + )] = − ( + + ) = −
 2 ∂2
i ∂x 2
∂2
∂y 2
∂2
∂z 2
2
2m
∂2
∂x 2
∂2
∂y 2
∂2
∂z 2
2
2m ∆
 T = − 2m ∆
2

The potential energy of a particle depends on the position of the particle, thus the operator is
the multiplication by the potential function:
( x, y, z, t ) V ( x, y, z, t ) ⋅ψ ( x, y, z, t )
V̂ψ=
Following the Newtonian analogy, the total energy operator, indicated by H, is the sum of
the kinetic energy operator and the potential energy operator V̂ :
2
H=−
ˆ ∆ + Vˆ ⋅
2m
H is called the Hamiltonian.
Sample video about this topic: https://www.youtube.com/watch?v=cUUFIk0ISuY

Schrödinger equation
Schrödinger wrote his famous equation to describe the motion of the electron. This is the
fundamental equation of quantum mechanics. In this course we examine only the simplest
case, e.g. only time-independent potentials. Thus we study only the time-independent version
of the Schrödinger equation. This is the energy-eigenvalue equation:
 
Hˆ ψ (r ) = Eψ (r )
or in an other form:
2    
− ∆ϕ ( r ) + V ( r ) ϕ ( r ) = Eϕ ( r )
2m
This is a second order partial differential equation for the energy-eigenvalues and
eigenfunctions of the system. Any wave-function can be the stationary wave-function of the
system only if it is a solution of this energy-eigenvalue equation, thus the energy has a certain,
well defined value.
Thus if we want to examine the stationary behaviour of an electron, we must incorporate all
relevant interactions into the potential energy term and then solve the Schrödinger equation.
After that we can calculate the values of physical quantities represented by operators.

Heisenberg’s uncertainty principle

There is a fundamental limit to the precision with which certain pairs of physical properties of
a particle (or any system) can be known simultaneously. These pairs are known as
complementary variables, for example position x and momentum p.

∆x∆px ≥ 
2


∆y∆p y ≥
2
 Heisenberg uncertainty relations

∆z ∆pz ≥
2
 
∆E ∆t ≥ 
2 
Here the Greek letter Δ means the uncertainty, mathematically the (standard) deviation.
The uncertainty appears when the system is not in the eigenstate of the particular
operator. Heisenberg uncertainty relations state that there is no function which is an
eigenfunction of e.g. both the momentum and the position operator.
Historically, the uncertainty principle has been confused with a similar effect in physics,
called the observer effect, which notes that measurements of certain systems cannot be made
without affecting the systems. Heisenberg offered such an observer effect at the quantum
level as a physical "explanation" of quantum uncertainty. However, it has since become
clear that the uncertainty principle is inherent in the properties of all wave-like systems.
Thus, the uncertainty principle actually states a fundamental property of quantum
systems, and is not a statement about the observational success of current or future
technology.
The last inequality can be interpreted in case of stationary states as the following: if ψ is an
eigenfunction of the Hamiltonian, then the uncertainty of the energy is zero, thus the
uncertainty of the time must be infinity, therefore this state can persist forever, which means
that the state is stationary.

Free particle in 1D

The simplest case is when the potential V is zero everywhere. Then the potential term is
missing from the Schrödinger equation, thus we get:
 2 ∂ 2ϕ ( x)
− Eϕ ( x)
=
2m ∂x 2
we can rearrange it:
d 2ϕ 2mE
= − 2 ϕ
dx 2

2mE
and introduce new notation: k = . Now the equation it is very simple:

d 2ϕ
2
= −k 2ϕ
dx
The solution:

ϕ ( x) = Aeikx ,
where k is an arbitrary real number. Let us calculate the momentum:
 ∂
pˆ xϕ =
i ∂x
( 
)
Aeikx = ⋅ ik ⋅ Aeikx = kϕ
i
thus momentum of the particle is
h
=
p =
k
λ
and we get back the assumption of de Broglie. Now we can write the wave-function into an
other form:
i
ϕ ( x ) = Ae 
px x

We obtain the energy of the particle similarly:

 2 ∂ 2ϕ ( x) 2 ∂ 2
−
2m ∂x 2
=
−
2m ∂x 2
(
Aeikx 2k 2
==
2m
)ϕ ( x) Eϕ ( x)

Thus the energy is:

2k 2
E=
2m
As k was an arbitrary real number, the energy of the free particle can be any positive number,
so the energy-spectrum is continuous. If k>0, the momentum and therefore the velocity of
the particle is positive, which means that the particle is travelling to the right. The particle can
be in a superposition of a left-moving and a right moving wave:

ϕ ( x) Aeikx + Be-ikx
=
This is also a solution of the Schrödinger equation above, because only k2 is present in the
expression of energy.
If A=B, then the above solution can be given in a new form using the Euler identity
=
eix cos x + i sin x :
ϕ ( x) = A(eikx + e −ikx ) = 2 A cos kx .
Similarly, if A = − B :
ϕ ( x) = A(eikx − e −ikx ) = 2 A sin kx .
Thus the sin and cos functions are also good solutions of the energy-eigenvalue
equation, and they represent standing waves.

Infinite 1D potential well (particle in a box)

We solve this problem only in 1D, where the potential limits the motion of the particle into the
( 0, a ) interval:
∞, if x < 0

=
V ( x) 0, if 0 ≤ x ≤ a
∞, if x > a


Thus outside the ( 0, a ) interval, ϕ ≡ 0 .

Now we have a nontrivial continuity requirement:
ϕ=
(0) ϕ=
(a) 0
Inside the well, (in the 0 ≤ x ≤ a section) the Schrödinger-equation has the form:
 2 d 2ϕ
− Eϕ
=
2m dx 2
It is very similar to the case of the free particle. However, the absolute value of the e±ikx
function is 1, thus these functions never reach zero, which contradicts the continuity
requirement. We can write the general solution of this equation:
ϕ = A ⋅ sin ( kx ) + B ⋅ cos ( kx ) .
The continuity requirement ϕ (0)=0 yields B=0, thus the wave function is purely a sine wave.
ϕ (a)=0 yields:

Asin ( ka ) =0 ,
⇔ ka =nπ
where n is an integer number, which will be our first quantum number.
nπ
So we have the wave function: ϕ n = A sin x
a
Physically this means a standing wave for each n>0. In order to obtain the possible energy
2mE
values we substitute back the expression k = , and obtain:


2mE
a = nπ .

After rearrangement
h2
2mEa 2 = n 2 π 2 h 2 = n 2 π 2
4π 2
One can see that the energy is quantized and proportional to the square of the n quantum
number:
h2
E= 2
n2
8 ma
See for example: https://www.youtube.com/watch?v=nFHhLJGDNHA

Solution of Schrödinger equation for a step potential

Suppose that at x=0 there is a discontinuity in the potential:

0, if x < 0
V ( x) = 
V, if 0 ≤ x
We examine the case when a particle is coming from the left side with kinetic energy less than
V.

As a particle approaches the barrier, it is described by a free particle wavefunction. The

solution of the Schrödinger equation on the left side is usual:
− i px x
ϕ1 ( x ) =
i p x
Ae  x + Be , px > 0
The second term represents the reflected wave, thus B ≤ A .
When it reaches the barrier, it must satisfy the Schrödinger equation in the form
 2 d 2ϕ
− + Vϕ = Eϕ .
2m dx 2
If we introduce=
q 2m(V − E ) > 0 and rearrange the equation:
d 2ϕ q 2
= ϕ
dx 2  2
Now the mathematical solution is a combination of exponential functions with real exponent:
q q
− x x
ϕ (x) Ce
= 
+ De

The second term is problematic:
q
x
e 
→ ∞, if x → ∞ , which is nonphysical. Thus D=0 and the solution is an
exponentially decreasing real function:
q
− x
ϕ2 ( x ) = Ce 

The probability density

−2 q − 8 m (V − E )
x x
ρ ( x) = φ ( x) ⋅ φ ( x) = C ⋅ C ⋅ e = C ⋅e
2
* *  

According to classical physics, a particle of energy E less than the height V of a barrier could
not penetrate - the region inside the barrier is classically forbidden. But the wavefunction
associated with a free particle must be continuous at the barrier and will show an exponential
decay inside the barrier.
The penetration depth is the distance inside the potential-step where the probability
decreases by a factor e:
ρ (x p ) = e−1ρ (x 0 )
Now the penetration depth is inversely proportional to the square root of the mass and the
missing energy:

xp = ,
8m(V − E )
and with this notation:
x
−
ρ (=
xp
x) C ⋅ e
2

Quantum Tunnelling
Consider now a potential barrier: E

V0
0, if x < 0

=
V ( x) V, if 0 ≤ x ≤ a E
0, if x > a

0 a

Let examine a particle coming from the left with kinetic energy less than V.
As the left part of the potential is the same as in the previous case, we use the information
obtained for the step potential. Most importantly the wave function inside the barrier is an
exponentially decreasing function. The wavefunction must be continuous at both side of the
barrier, so there is a finite probability that the particle will tunnel through the barrier. If this
happens, the energy of the particle will be the same as before meeting the potential barrier.

The transmission coefficient T and reflection coefficient R are used to describe the behaviour
of waves incident on a barrier. The transmission coefficient represents the probability of the
particle to cross the barrier.
a
−
a 8m (V − E )
ρ (a) C ⋅ e
2 xp
−  a
=
T = = e=
x
e p 
ρ (0) C
2
while R = 1 − T .

Thus in quantum mechanics, the particle can go across energy barriers which – according to
classical physics – too high and therefore impenetrable for them. This is a manifestation of
Heisenberg’s uncertainty principle. However, as the size of the particle or the width of the
potential barrier is increasing, the probability of violating classical physics is rapidly
decreasing.

Examples:

Tunnelling occurs with barriers of thickness around 1-3 nm and smaller, but it is the cause of
some important macroscopic physical phenomena. For instance, tunnelling is a source of
current leakage in very-large-scale integration (VLSI) electronics and results in the
substantial power drain and heating effects that plague high-speed and mobile technology; it is
considered the lower limit on how small computer chips can be made.

Nuclear fusion
Fusion occurs in most stars like the Sun. The temperatures in the Sun are actually many times
cooler than the extreme high temperatures which are theoretically needed to provide the
incoming protons with enough energy and speed to overcome the strong repulsive
electromagnetic force of the receiving hydrogen atoms. By virtue of quantum tunnelling and
Heisenberg’s uncertainty principle, the protons can tunnel through the barrier even given the
apparently insufficient temperature and energy. The probability of this tunnelling is quite low,
that is why the sun shines approximately constantly over several millions of years.
Radioactive decay
Radioactive decay is the process of emission of particles and energy from the unstable
nucleus of an atom to form a stable product. This is done via the tunnelling of a particle out
of the nucleus. This was the first application of quantum tunnelling.

Cold emission
Cold emission of electrons is relevant to semiconductors and superconductor physics. It is
similar to thermionic emission, where electrons randomly jump from the surface of a metal to
follow a voltage bias because they statistically end up with more energy than the barrier,
through random collisions with other particles. When the electric field is very large, the
barrier becomes thin enough for electrons to tunnel out of the atomic state, leading to a
current that varies approximately exponentially with the electric field. These materials are
important for flash memory, vacuum tubes, as well as some electron microscopes.

Tunnel junction
A simple barrier can be created by separating two conductors with a very thin insulator.
These are tunnel junctions, the study of which requires quantum tunnelling. For example
when you twist two copper wires together or close the contacts of a switch, current passes
from one conductor to the other despite a thin insulator oxide layer between them. The
electrons go through this thin insulating layer by the tunnel effect. If there are only a few
atomic layers between the two conductors, the tunnelling probability is enough for
conducting.
In case of superconductors, Josephson junctions take advantage of quantum tunnelling.

Tunnel diode
A tunnel diode is a type of semiconductor device that is capable of very fast operation, well
into the microwave frequency region, made possible by the use of the quantum tunneling.
There is a voltage-region where the differential resistance is negative because the current
decreases with increasing voltage.

Angular momentum in quantum physics

The angular momentum operator plays an important role in the theory of atomic physics and
other quantum problems involving rotational symmetry.
In classical physics:
  
L= r × p
This can be carried over to quantum mechanics, by reinterpreting r as the quantum position
operator and p as the quantum momentum operator. L is then an operator, specifically called
the orbital angular momentum operator. Specifically, L is a vector operator, meaning
L = ( Lx , Ly , Lz ) , where Lx, Ly, Lz are three different operators.

However, there is another type of angular momentum, called spin angular momentum
(more often shortened to spin), represented by the spin operator Ŝ .
Because of the Heisenberg’s uncertainty principle, the x, y and z component of the angular
momentum cannot be measured simultaneously, they have no definite values at the same
time. If Lz and L2 is determined (these two are the usual choice), than Lx and Ly are
completely undetermined. So it is possible to solve only the Lz and L2 eigenvalue-equation
simultaneously to obtain the possible values for the angular momentum.
The orbital angular momentum is quantized according to the relationship:
L2 =  2 l (l + 1)
where l = 0,1,2,... is the angular or azimuthal quantum number.
The z-component of the angular momentum takes the form
Lz = m , where m =−, −  + 1,..., 0,1, 2, ...,  − 1,  is the magnetic quantum
number
As these formulas can be derived from a very general way, these applies to orbital angular
momentum, spin angular momentum, and the total angular momentum for an atomic system.
We recall that angular momentum quantization was put into the semi-classical Bohr model
as an ad hoc assumption with no fundamental justification and the concrete Le− = n 
formula was not correct. However, by the real quantum mechanics, the quantization and the
correct values come out automatically.

Quantum numbers in an atom contains 1 electron

  
From the Heisenberg’s uncertainty relation ∆x∆px ≥ we obtain ∆x ⋅ m ⋅ ∆vx ≥ ≈ 10−34
2 2
For the electron in the atom, the uncertainty of the position is roughly the size of the atom:
∆x ≅ 10 −10 m and the mass is m ≅ 10−30 kg , thus
10−34 m
∆vx ≅ −10 −30
=
106 .
10 ⋅10 s
This is so high that we can state that the electron has no trajectory in the atom. If we
would localize the electron even more, the uncertainty is even higher.
We need to find a more relevant and usable description and it is possible with quantum
numbers.
We have to solve the Schrödinger-equation with the Coulomb-potential:
2 Ze 2
− ∆ψ − k ψ=Eψ ;
2m r
The solution consists of complicated functions, where the quantum numbers are the
parameters of these functions.

1. The principal quantum number (n) describes the electron shell, or energy level, of
an atom. The value of n ranges from 1 to the shell containing the outermost electron of
that atom, i.e.
1
Εn =
−Z 2 ⋅ E* ⋅ , where n = 1, 2, ...
n2
2. The angular or azimuthal quantum number (ℓ) (also known as the orbital quantum
number) describes the subshell, and gives the magnitude of the orbital angular
momentum through the relation
=
L2  2 ( + 1) , where ℓ = 0, 1, 2,..., n − 1.
"ℓ = 0" is often called an s orbital, "ℓ = 1" a p orbital, "ℓ = 2" a d orbital, and "ℓ = 3" an
f orbital.
3. The magnetic quantum number (m) describes the specific orbital (or "cloud") within that
subshell, and yields the projection of the orbital angular momentum along a specified
axis:
Lz = m , where m =−, −  + 1,..., 0,1, 2, ...,  − 1, 
As the magnetic moments have a potential energy in magnetic field (this is the Zeeman-

energy), if H ≠ 0 then the energy of the electron depends on H as well.
4. The spin quantum number or more precisely the spin projection quantum number (ms or
sometimes s) describes the spin (intrinsic angular momentum) of the electron within that
orbital, and gives the projection of the spin angular momentum S along the specified
axis:
Sz = ms where ms = 1 1
− ,+
2 2
https://www.youtube.com/watch?v=GordTWgyQnA

Quantum Statistics

In statistical mechanics, the classical or Maxwell–Boltzmann statistics describes the

average distribution of distinguishable particles over various energy states in thermal
equilibrium if quantum effects are negligible. The expected number of particles in a state
with energy Ei
E
1 1 − kTi
f MB=
(Ei ) = Ei
e ,
A
Ae kT
where k is Boltzmann's constant, T is the absolute temperature, A is a normalization
constant (which keeps the number of particles constant).

In quantum statistics, there are two possible ways in which a collection of non-
interacting indistinguishable particles may occupy a set of available discrete energy
states, at thermodynamic equilibrium. One of them is the Bose–Einstein statistics (B–E
statistics) and the other is the Fermi–Dirac statistics.

The Bose–Einstein statistics apply only to those particles not limited to single
occupancy of the same state — that is, particles that do not obey the Pauli exclusion
principle restrictions. Such particles have integer values of spin and are named bosons,
after the statistics that correctly describe their behaviour. If we have a state i with energy
Ei , then the average number of particles in that state is
1
fBE (Ei ) = Ei
Ae kT −1
Examples for bosons are the photons, the He nucleus and the Higgs boson.
The other statistics is Fermi–Dirac statistics, which describes a distribution of particles
over energy states in systems consisting of particles that obey the Pauli exclusion
principle. It is most commonly applied to electrons, protons and neutrons, which
are fermions with spin 1/2. If we have a state i with energy Ei , then the average number
of Fermi particles in that state is

1
fFD (Ei ) = Ei
Ae kT +1
E
− F
It can be calculated that the normalization constant A is A = e kT , where EF is the
Fermi energy. Now we have:
1
fFD (Ei ) = Ei − EF
e kT +1
( )
The denominator cannot be less than one, f Ei < 1 , thus one can see that it reflects
the Pauli principle. Therefore we can say f ( Ei ) is the probability of occupying the
particular state.

Even if the temperature is absolute zero, the fermions cannot occupy the state with the
minimal energy, because they are already occupied by other fermions.
At low temperatures, bosons can behave very differently than fermions because an
unlimited number of them can collect into the same energy state, a phenomenon called
"condensation".
E
kT
If the energy E is much larger than kT, the e term is much greater than 1, thus the
quantum statistics tend to the classical one.

Quantum numbers for atoms with more electrons and the

periodic table

It is very hard to solve the Schrödinger equation if the number of electrons is greater
than one. The results will be similar to the case of one electron, but now the quantum
numbers have no exact meaning, they describe the behaviour of the electrons only
approximately. The most important difference from the one-electron case is that now the
energy depends on the angular quantum number:
E n, <E n, +1
The order of the energy levels:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p

To understand the periodic table, we need the Pauli principle and the energy-minimum
principle applied to these concrete energy-levels.
An element's location on the periodic table reflects the quantum numbers of the last
orbital filled. The period indicates the value of principal quantum number for the
valence shell. The lanthanides and actinides, indicated by pink-purple, are in periods 6
and 7, respectively. Each of them contains 14 elements, because if  = 3 , m has 7
possible values (from -3 to 3), and 2*7=14.
The block indicates the value of the angular quantum number  for the last subshell
that received electrons in building up the electron configuration. The blocks are named
for subshells (s, p, d, f)
 Each block contains a number of columns equal to the number of electrons that can
occupy that subshell
The s-block (in light blue) has 2 columns, because a maximum of 2 electrons can
occupy the single orbital in an s-subshell.
The p-block (in green) has 6 columns, because a maximum of 6 electrons can
occupy the three orbitals in a p-subshell.
The d-block (in orange) has 10 columns, because a maximum of 10 electrons can
occupy the five orbitals in a d-subshell.
The f-block (in pink/purple) has 14 columns, because a maximum of 14 electrons
can occupy the seven orbitals in a f-subshell.
Possible elaborative questions:

1) Blackbody radiation
2) Photoelectric effect and the momentum of the photon
3) Line spectra of atoms and the Bohr model
4) Wave particle duality of particles, de-Broglie hypothesis
5) Wave Function and the principle of superposition
6) Operators and eigenvalues
7) The concrete form of the operators and the Schrödinger equation
8) Heisenberg’s uncertainty principle
9) Free particle in 1D
10) Infinite 1D potential well (particle in a box)
11) Solution of Schrödinger equation for a step potential and quantum tunnelling
12) The essence of quantum tunnelling and some examples
13) Angular momentum and atoms with 1 electron
14) Quantum Statistics
15) Atoms with more electrons and the periodic table

Sample questions:

Which is true for the photoelectric effect?

A) If the incoming intensity is large, the effect always immediately
occurs.
B) The effect occurs only if the frequency is large enough.
C) We can always see the effect independently of the frequency of the
light.
D) The energy of the incoming photon is always smaller than the energy
of the emitted electron.
E) The effect occurs only in the case of some discrete frequencies.
F) If the incoming intensity is small, we have to wait for the effect for
hours or days.
Which one in not true for the wave function of a given electron in a given
infinite potential well?
A) It is continuous.
B) It is zero at the edge of the wall.
C) It can be zero in some points inside the well far from the edges.
D) The energy can be arbitrary.
E) The kinetic energy is positive.
F) The energy can be determined without deviance.