APH306 Atomic Physics © 2024

Lecture 1

1.0Atomic Physics

What is atomic physics?

It is the branch of physics concerned with the structure of the atom and the characteristics of
subatomic particles. (noun from oxford).

A model is a mental picture of how atom is thought to look like. We have various models of atom
presented by different scientist depending on the level of technology development,

Atomic physics is the field of physics that studies atoms as an isolated system of electrons and
an atomic nucleus. It is primarily concerned with the arrangement of electrons around the
nucleus and the processes by which these arrangements change. It’s assumed that the
term atom includes ions – charged atoms and neutral atoms. (from Wikipedia)

Distinction between atomic physics and Nuclear physics.

Atomic physics deals with the atom as a system consisting of a nucleus and electrons.

Nuclear physics deals atomic nuclei, their constituents and how they interact.

Isolated atoms
When considering atoms in isolation, atomic models will consist of a single nucleus that may be
surrounded by one or more bound electrons. It is concerned with processes such
as ionization and excitation by photons or collisions with other atomic particles. Atomic physics
is not concerned with the formation of molecules nor does it examine atoms in a solid state as
in condensed matter.

History and developments

Democritus (6th century BC to 2nd century BC)

One of the earliest steps towards atomic physics was the recognition that matter was composed
of atoms. He suggested that all things are made up of tiny invisible and indivisible particles.

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Atom is the smallest particle that an element can be divided into and still remain the same element.
Arrangement of these atoms determine the chemical and the physical characteristics of an element.

His proposal could not be verified experimentally. This theory was later developed in the modern
sense of the basic unit of a chemical element by the British chemist and physicist John Dalton in
the 18th century.

John Dalton (1776-1844)

His theory dealt with how elements combine to form new substances.

The main points of Dalton's atomic theory, as it eventually developed, are:

1. Elements are made of extremely small particles called atoms.

2. Atoms of a given element are identical in size, mass and other properties; atoms of different
elements differ in size, mass and other properties.
3. Atoms cannot be subdivided, created or destroyed.
4. Atoms of different elements combine in simple whole-number ratios to form chemical
compounds.
5. In chemical reactions, atoms are combined, separated or rearranged.

The invention of the periodic system of elements by Mendeleev was another great step forward.

J. J. Thomson’s Atomic Model (1856-1940)

He discovered the electrons from the cathode ray tube.

British physicist J. J. Thomson in 1898 suggested that every atom is uniformly positive charged
sphere of radius of the order of 10−10 𝑚 , in which entire mass is uniformly distributed and
negative charged electrons are embedded randomly. The atom as a whole is neutral.

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The atomic stability was brought by electrons being held strongly by electrostatic forces. He sees
an atom as a homogeneous sphere of positive charges inside of which negatively charged electrons
are attached. This model of the atom was given the rather unlikely name of ‘’plum pudding
model’’.

Limitations of Thomson's Atomic Model

1. It could not explain the origin of spectral series of hydrogen and other atoms.
2. It could not explain large angle scattering of a- particles.

Ernest Rutherford (1871-1937)

He was a student of J. J Thomson. He discovered alpha particles that are positively charged
particles emitted from radioactive elements.

The Rutherford scattering experiment showed Thomson's Atomic Model to be incorrect. At the
suggestion of Ernest Rutherford, Geiger and Marsden placed a sample of an alpha-emitting
substance behind a lead screen with a small hole in it, as in Fig below so that a narrow beam of
alpha particles was produced. This beam was directed at a thin gold foil. A zinc sulfide screen,
which gives off a visible flash of light when struck by an alpha particle, was set on the other side
of the foil with a microscope to see the flashes.

Rutherford's Atomic Model (also known as Nuclear model)

On the basis of this experiment, Rutherford made following observations:

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i) The entire positive charge and almost entire mass of the atom is concentrated at its centre in a
very tiny region of the order of 10−15 𝑚.
ii) The negatively charged electrons revolve around the nucleus in different orbits.
iii) The total positive charge nucleus is equal to the total negative charge on electron. Therefore,
atom as an overall is neutral.
iv) The centripetal force required by electron for revolution is provided by the electrostatic force
of attraction between the electrons and the nucleus.

Limitations of Rutherford Atomic Model

i) About the Stability of Atom According to Maxwell’s electromagnetic wave theory electron
should emit energy in the form of electromagnetic wave during its orbital motion. Therefore.
radius of orbit of electron will decrease gradually and ultimately it will fall in the nucleus.
ii) About the Line Spectrum Rutherford atomic model cannot explain atomic line spectrum.

Niels Bohr Model

He proposed the atomic orbital model.

The true beginning of atomic physics is marked by the discovery of spectral lines and attempts to
describe the phenomenon, most notably by Joseph von Fraunhofer. By 1814, Fraunhofer had
invented the modern spectroscope. The study of these lines led to the Bohr atom model and to the
birth of quantum mechanics. In seeking to explain atomic spectra an entirely new mathematical
model of matter was revealed. As far as atoms and their electron shells were concerned, the atomic
orbital model was proposed. This provided a new theoretical basis for quantum mechanics
and spectroscopy.

The origins of atomic physics started with the first model of the hydrogen atom by Bohr.

Early ideas, includes Einstein’s treatment of the interaction of atoms with radiation and classical
treatment of the Zeeman effect were intuitive way of thinking about atomic structure.

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Other Models

Summerfield (Somerfield) relativistic atom.

Modern Theory ; Electron cloud theory (Quantum theory of an atom).

Vector model of an atom.

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Lecture 2
2.0 ATOMIC SPECTRA

Spectroscopy
Spectroscopy is the study of the interaction between matter and electromagnetic radiation. Hot
Elements (liquids and dense gases) emit light with a continuous spectrum of wavelengths.

Spectrum is an ordered array of waves either in the order of frequencies or wavelength. We have
absorption spectrum and emission spectrum.

Spectroscopy – using a prism or diffraction grating to disperse the light inside a spectrograph
shows that the characteristic spectrum for atoms is composed of discrete lines that are the
‘fingerprint’ of the element.

The spectrum of light emitted by each element is unique and it’s a charcterictic pf a particular
atom. Spectroscopy is fundamental exploratory tool in the fields of physics, chemistry,
and astronomy, allowing the composition, physical structure and electronic structure of matter to
be investigated at atomic scale, molecular scale, macro scale, and over astronomical distances.

Fraunhofer (1880s) used a spectrograph (- an apparatus for photographing or otherwise recording

spectra) to measure the wavelength of lines in light from the sun.

Optical spectrometer is an instrument used in spectroscopy for producing spectral lines and
measuring their wavelengths and intensities.

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J. Rydberg Formula
The Rydberg formula is a mathematical formula used to predict the wavelength of light resulting
from an electron moving between energy levels of an atom. In 1888, the Swedish Professor J.
Rydberg found that the spectral lines in hydrogen obey the following mathematical formula where
𝑧 = 1:

1 1 1
= 𝑅 ( 2 − 2)
𝜆 𝑛 𝑚

where n and 𝑚 are whole numbers; R is a constant that has become known as the Rydberg constant.
1
λ is the wavelength of the photon and wavenumber = 𝜆.

When the electron changes from an orbital with high energy to a lower energy state, a photon of
light is created. When the electron moves from low energy to a higher energy state, a photon of
light is absorbed by the atom.

Hydrogen atomic spectra

An evacuated glass tube is filled with hydrogen (or some other gas) at low pressure. A large voltage
is applied between metal electrodes in the tube to produce an electric current in the gas, the tube
emits light having a color that depends on the gas inside.

When the emitted light is analyzed with a spectrometer, discrete

bright lines are observed, each having a different wavelength,
or color. Such a series of spectral lines is commonly called an
emission spectrum color.

The wavelengths contained in such a spectrum are

characteristic of the element emitting the light. Because no two
elements emit the same line spectrum, this phenomenon
represents a marvelous and reliable technique for identifying
elements in a gaseous substance.

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Above shows line spectra produced by emission in the visible range for the elements hydrogen,
mercury, and neon.

Hydrogen atom has the simplest spectrum. Only four lines are visible to the human eye. From
right to left in above fig. , these lines are: red (656 nm) called the H- α line; aqua (486 nm), blue
(434 nm), and violet (410 nm). There are infinitely many invisible spectral lines inthe series for
hydrogen. The lines with wavelengths shorter than 400 nm appear in the ultraviolet part of
the spectrum (far left) and are invisible to the human eye.

Emission spectra of the elements have complex structures; they become even more complex for
elements with higher atomic numbers.

The Rydberg formula may be applied to hydrogen to obtain its spectral lines. Setting 𝑛 to 1 and
running 𝑛′ from 2 to infinity yields the Lyman series.

The series of spectral lines for which n = 2 and 𝒎 = 3, 4, . .. is now called the Balmer series and
lies in the visible region of the spectrum. Johann Balmer was a Swiss mathematician who wrote
down an expression which was a particular case with n = 2, a few years before Johannes Rydberg
found the general formula that predicted other series. The first line at 656 nm is called the Balmer-
α (n =1 and 𝒎 = 3) line and it gives rise to the distinctive red colour of a hydrogen discharge.
The next line in the series is the Balmer-β (n = 2 to 𝒎 = 4) line at 486 nm in the blue and
subsequent lines at shorter wavelengths tend to a limit in the violet region.

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𝒏 𝒎 Converges Toward Name

1 2 → ∞ 91.13 nm (ultraviolet) Lyman series

2 3 → ∞ 364.51 nm (visible light) Balmer series

3 4 → ∞ 820.14 nm (infrared) Paschen series

4 5 → ∞ 1458.03 nm (far infrared) Brackett series

5 6 → ∞ 2278.17 nm (far infrared) Pfund series

6 7 → ∞ 3280.56 nm (far infrared Humphreys series

The transitions from higher shells n = 2, 3,

4, . . . down to the n = 1 shell give the
Lyman series of spectral lines.

Example

Find the wavelength of the electromagnetic radiation that is emitted from a hydrogen electron that
relaxes from n = 3 to n = 1. Given that Rydberg constant 𝑅 = 1.9074 𝑥 10−7 𝑚−1 . Give your
answer in nanometers and in Angstroms Å.

Solution

1 1 1 1 1
= 𝑅 ( 2 − 2 ) = (1.9074 𝑥 107 ) ( 2 − 2 ) → 𝜆 = 1.9072 𝑥 10−7 𝑚 = 190.7 𝑛𝑚
𝜆 𝑛 𝑚 1 3
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Example

Calculate the longest and the shortest wavelengths in the Balmer series.

Solution

The long-wave limit;

1 1 1 1 1
= 𝑅 ( 2 − 2 ) = (1.9074 𝑥 107 ) ( − ) ⟹ 𝜆 = 656.3 𝑛𝑚
𝜆 2 3 4 9

The short-wave limit;

1 1 1 1
= 𝑅 ( 2 − 2 ) = (1.9074 𝑥 107 ) ( − 0) ⟹ 𝜆 = 364.6 𝑛𝑚
𝜆 2 ∞ 4

Example

Calculate the wavelength of the lowest-energy line in the Lyman series to three significant figures.
In what region of the electromagnetic spectrum does it occur?

Solution

A For the Lyman series, n = 1. The lowest-energy line is due to a transition from the 𝑚 = 2 to
𝑛 = 1 orbit because they are the closest in energy.

1 1 1 1 1
= 𝑅 ( 2 − 2 ) = (1.9074 𝑥 10−7 ) ( − ) = 8,228 𝑥 106 𝑚−1
𝜆 1 2 4 9

⟹ 𝜆 = 1.215 𝑥 10−7 = 122 𝑛𝑚

Exercise

The Pfund series of lines in the emission spectrum of hydrogen corresponds to transitions from
higher excited states to the 𝑛 = 5 orbit. Calculate the wavelength of the second line in the Pfund
series to three significant figures. In which region of the spectrum doesit lie? 𝐴𝑛𝑠 4560 𝑛𝑚
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Lecture 3

3.0 Bohr’s Theory of an Atom

Niels Bohr proposed the Bohr Model of the Atom in 1915. Model has an atom consisting of a
small, positively-charged nucleus orbited by negatively-charged electrons. This is similar to the
planets orbiting the Sun. The gravitational force of the solar system is mathematically akin to the
Coulomb (electrical) force between the positively-charged nucleus and the negatively-charged
electrons.

It was already known from Rutherford’s experiments that inside atoms there is a very small,
dense nucleus with a positive charge .

Bohr assumed that each electron orbits the nucleus in a circle, whose radius r is determined by the
balance between centripetal acceleration and the Coulomb attraction towards the proton. For
electrons of mass 𝑚𝑒 and speed 𝑣 this gives:

𝑚𝑒 𝑣 2 𝑒2 𝑒2
=𝑘 2=
𝑟 𝑟 4𝜋𝜀0 𝑟 2

This leads to the following relation between the angular frequency 𝜔 = 𝑣/𝑟 and the radius:

𝑚𝑒 𝑣 2 1 𝑒2 1 𝑣2 2
𝑒2
𝑥 = 2
𝑥 ⟹ = 𝜔 =
𝑟 𝑟 4𝜋𝜀0 𝑟 𝑟 𝑟2 4𝜋𝑚𝑒 𝜀0 𝑟 3

The total energy of an electron in such an orbit is the sum of its kinetic and potential energies:

1 𝑒2
𝐾. 𝐸 = 𝑚𝑒 𝑣 2 −
2 4𝜋𝜖0 𝑟

Kinetic energy has a magnitude:

1 2
1 𝑒2 1 𝑒2
𝐾. 𝐸 = 𝑚𝑒 𝑣 = ( ) ≡ 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 =
2 2 4𝜋𝜖0 𝑟 2 8𝜋𝜖0 𝑟

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Total energy is therefore given by:

𝑒2
𝐸𝑇 = −
8𝜋𝜀0 𝑟

This total energy is negative because the electron is bound to the proton and energy must be
supplied to remove it. There are certain allowed orbits for which the electron has a fixed energy.
The electron loses energy only when it jumps between the allowed orbits and the atom emits this
energy as light of a given wavelength.

Electrons in the allowed orbits do not radiate energy which is contrary to classical electrodynamics
where a charged particle in circular motion undergoes acceleration and hence expected to radiates
electromagnetic waves.

The next big question is which out of all the possible classical orbits are the allowed ones? Bohr
introduced a major assumption that the only orbits that will be occupied are those with angular
ℎ
momentum which is an integral multiple of reduced planks constant ℏ = .
2𝜋

We start by quantization of the angular momentum to be in terms of integral multiples of ℏ (ℏ =

Planck’s constant over 2π):

𝑚𝑒 𝑣𝑟 = 𝑛ℏ

where n is an integer. The making velocity the subject;

𝑛ℏ 2
𝑛 2 ℏ2
𝑣= → 𝑣 = 2 2
𝑚𝑒 𝑟 𝑚𝑒 𝑟

Substitute this in the equation of centripetal and Coulomb’s force we get the radii 𝑟 as;

2
𝑛 2 ℏ2 𝑚𝑒 𝑣 2 𝑒2
𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦, 𝑣 = 𝑖𝑛𝑡𝑜 =
𝑚𝑒2 𝑟 2 𝑟 4𝜋𝜀0 𝑟 2

𝑒2 1 𝑒2 𝑚𝑒2 𝑟 2 𝑛2 ℏ2 4𝜋𝜀0
𝑟= ∙ ⟹𝑟= ∙ ⟹𝑟=
4𝜋𝑚𝑒 𝜀0 𝑣 2 4𝜋𝑚𝑒 𝜀0 𝑛2 ℏ2 𝑚𝑒 𝑒 2

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ℏ2 4𝜋𝜀0 2 2
ℏ2 4𝜋𝜀0
𝑟= ∙ 𝑛 𝑠𝑖𝑚𝑙𝑖𝑓𝑖𝑒𝑑 𝑎𝑠 𝑟 = 𝑎0 𝑛 𝑤ℎ𝑒𝑟𝑒 𝑎0 =
𝑚𝑒 𝑒 2 𝑚𝑒 𝑒 2

Radius is also quantized:

𝑟 = 𝑎0 𝑛 2

where the Bohr radius 𝑎0 is given by:

4𝜋𝜀0 ℏ2
𝑎0 =
𝑚𝑒 𝑒 2

Bohr’s radius is a natural unit of length in atomic physics.

Electron charge, e = 1.602 x 10-19 C

Permittivity of free space, 𝜀0 = 8.85 𝑥 10−12 C2 /Nm2

Planck Constant, ℎ = 6.6256 𝑥 10−34 J/s

ℎ 6.6256 𝑥 10−34
Reduced planks constant, ℏ = = = 1.055 𝑥 10−34 J/s
2𝜋 2𝜋

Mass of an electron, me = 9.1 x 10-31 kg

1Å = 10−10 𝑚

4𝜋𝜀0 ℏ2 4𝜋( 8.85 𝑥 10−12 )(1.055 𝑥 10−34 J/s )2 1.11 𝑥 10−78

𝑎0 = = -31 = = 5.299 𝑥 10−11 𝑚
𝑚𝑒 𝑒 2 (1.602 x 10 ) (9.1 x 10 )
-19 2 2.1 𝑥 10 −68

𝑎0 = 5.29 𝑥 10−11 = 5.29 𝑥 10−1 𝑥 10−10 = 0.529 𝑥 10−10 = 0.529 Å

𝑎0 = 5.29 𝑥 10−11 = 5.29 𝑥 10−2 𝑥 10−9 = 0.0529 𝑥 10−9 = 0.0529 𝑛𝑚

When this radius is substituted in the energy function we have the famous Bohr’s energy formula;

𝑒2 𝑒2 𝑒2
𝐸𝑇 = − =− ⟹ 𝐸𝑇 =
8𝜋𝜀0 𝑟 8𝜋𝜀0 (𝑎0 𝑛2 ) 8𝜋𝜀0 𝑎0 𝑛2
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Appearance of integer 𝑛 in the expression of energy indicated that energy is also quantized.

The positive integer 𝑛 is called the principal quantum number.

When the quantum number 𝑛 = 1:

𝑒2 (1.602 x 10 -19 )2 2.3 𝑥 10−28

𝐸𝑛=1 = = − = −
8𝜋𝜀0 𝑎0 𝑛2 8𝜋( 8.85 𝑥 10−12 )(5.29 𝑥 10−11 )(𝑛2 ) 1.06 𝑥 10−10

𝐸𝑛=1 = −2.16 𝑥 10−18 𝐽

2.16 𝑥 10−18
𝐸𝑛=1 = − = −13.56 𝑒𝑉
1.6 𝑥 10−19

If 𝐸𝑛=1 = 𝐸0 , other energy levels for 𝑛 = 2, 3 4 can be obtained as;

𝐸0
𝐸𝑛=1 =
𝑛2

We have discrete energy levels;

𝐸0 𝐸0 𝐸0 𝐸0
𝐸0 , , , , … , = 0 (𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑛𝑜𝑡 𝑏𝑜𝑢𝑛𝑑)
4 9 16 ∞

Hydrogen-like Atoms

The simplest example of the Bohr Model is for the hydrogen atom (𝑍 = 1) in which a negatively-
charged electron orbits a small positively-charged nucleus. Discussion this far is about one electron
and a one proton system which is the case in hydrogen atom. The energy expression for hydrogen-
like atoms (with only one electron) is a generalization of the hydrogen atom energy, in which Z is
the nuclear charge.

The value of 𝑧 = +1 for hydrogen, 𝑧 = +2 for He, 𝑧 = +3 for Li, and so on. The total positive
charge is equal to the total negative charge to have Hydrogen-like atoms. The value of 𝐾 =
2.179 × 10–18 𝐽.

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𝑧𝑒 2 1 −18
𝑧 𝑧
𝐸𝑛=1 = − = − (2.174 𝑥 10 𝐽) = −𝑘
8𝜋𝜖0 𝑎0 𝑛2 𝑛2 𝑛2

Photon Emission explained using Bohr’s model

According to Bohr’s theory, there is no energy emission as long as an electron remains in the same
state (level) of energy. From the equation of radiation;

𝑐 ℎ𝑐
𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑒𝑛𝑒𝑟𝑔𝑦, ∆𝐸 = 𝐸𝑛=2 − 𝐸𝑛=1 = ℎ𝑓 = ℎ =
𝜆 𝜆

𝑒2 1 𝑒2 1 𝑒2 1 𝑒2 1 𝑒2 1 1
∆𝐸 = (− ) − (− ) = − = ( − )
8𝜋𝜖0 𝑎0 𝑛22 8𝜋𝜖0 𝑎0 𝑛12 8𝜋𝜖0 𝑎0 𝑛12 8𝜋𝜖0 𝑎0 𝑛22 8𝜋𝜖0 𝑎0 𝑛12 𝑛22

1 1 1 1
∆𝐸 = 2.174 𝑥 10−18 ( − ) = 𝑘 ( − )
𝑛1 𝑛2 𝑛1 𝑛2

Where 𝑘 = 2.174 𝑥 10−18 J

ℎ𝑐 1 1 1 𝑘 1 1
= 2.174 𝑥 10−18 ( − ) → 𝑤𝑎𝑣𝑒 𝑛𝑢𝑚𝑏𝑒𝑟, = ( − )
𝜆 𝑛1 𝑛2 𝜆 (ℎ𝑐) 𝑛1 𝑛2

Where Rydberg constant 𝑅 was calculated :

𝑘 (2.174 𝑥 10−18 )
𝑅= = = 1.135 𝑥 107
(ℎ𝑐) (6.63 𝑥 10−34 )(2.89 𝑥 108 )

Bohr managed to derive a theoretical expression for the Rydberg constant.

Bohr’s formula predicts that in the transitions between these energy levels the atoms emit light
with a wavenumber given by:

1 1 1
𝑣̅ = = 𝑅 ( 2 − 2)
𝜆 2 𝑛

Where 𝑣̅ is the wave number and 𝑅 is the Rydberg’s constant when the nucleus is fixed.

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Bohr Model for Heavier Atoms

Heavier atoms contain more protons in the nucleus than the hydrogen atom. More electrons were
required to cancel out the positive charge of all of these protons. Bohr believed each electron orbit
could only hold a set number of electrons. Once the level was full, additional electrons would be
bumped up to the next level. Thus, the Bohr model for heavier atoms described electron shells.
The model explained some of the atomic properties of heavier atoms, which had never been
reproduced before.

For example, the shell model explained why atoms got smaller moving across a period (row) of
the periodic table, even though they had more protons and electrons. It also explained why the
noble gases were inert and why atoms on the left side of the periodic table attract electrons, while
those on the right side lose them. However, the model assumed electrons in the shells didn't interact
with each other and couldn't explain why electrons seemed to stack in an irregular manner.

Main Points of the Bohr Model:

• Electrons orbit the nucleus in orbits that have a set radius and energy.
• The energy of the orbit is related to its radius. The lowest energy is found in the smallest
orbit.
• Radiation is absorbed or emitted when an electron moves from one orbit to another.

Bohr’s Key equations

𝑘𝑧 2
𝐸𝑛 = − , 𝑛 = 1,2,3, …
𝑛2
1 1
∆𝐸 = 𝑘𝑧 2 ( 2 − 2)
𝑛1 𝑛2
𝑛2
𝑟= 𝑎
𝑧 0
𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 𝑜𝑓 𝑎𝑛 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛, 𝑣 =

Problems with the Bohr Model

• It violates the Heisenberg Uncertainty Principle because it considers electrons to have both
a known radius and orbit.
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• The Bohr Model provides an incorrect value for the ground state orbital angular
momentum.

• It makes poor predictions regarding the spectra of larger atoms.

• It does not predict the relative intensities of spectral lines.

• The Bohr Model does not explain fine structure and hyperfine structure in spectral lines.

• It does not explain the Zeeman Effect.

Example

If a spark promotes the electron in a hydrogen atom into an orbit with n = 3, what is the calculated
energy, in joules, of the electron?

Solution

𝑧2 −18 )
12
𝐸𝑛 = −𝑘 = −(2.174 𝑥 10 = 2.421 𝑥 10−19 J
𝑛2 32

Example

If the electron is promoted even further to an orbit with n = 6. What is its new energy?

Solution

𝑧2 −18 )
12
𝐸𝑛 = −𝑘 2 = −(2.174 𝑥 10 = −6.038 𝑥 10−20 J
𝑛 62

Example

Calculate the energy (in joules) and the wavelength (in meters) of the line in the spectrum of
hydrogen that represents the movement of an electron from Bohr orbit with n = 4 to the orbit
with n = 6? Calculate the wavelength of the photon?

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Solution

1 1 1 1
∆𝐸 = 𝐸1 − 𝐸1 = (2.179 𝑥 10−18 ) ( 2 − 2 ) = (2.179 𝑥 10−18 ) ( 2 − 2 )
𝑛 𝑚 4 6

∆𝐸 = 7.566 𝑥 10−20 𝐽

This energy difference is positive, indicating a photon enters the system (is absorbed) to
excite the electron from the n = 4 orbit up to the n = 6 orbit.

ℎ𝑐 (6.63 𝑥 10−34 𝐽𝑠)(3 𝑥 108 𝑚/𝑠)

𝜆= = = 2.626 𝑥 10−6 𝑚
𝐸 7.566 𝑥 10−20 𝐽

Exercise

1. What is the energy in joules and the wavelength in meters of the photon produced when an
electron falls from the n = 5 to the n = 3 level in a He+ ion (Z = 2 for He+)?
Ans: 6.198 × 10–19 J; 3.205 × 10−7 m

2. What does it mean to say that the energy of the electrons in an atom is quantized?
Quantized energy means that the electrons can possess only certain discrete energy
values; values between those quantized values are not permitted.

3. Using the Bohr model, determine the energy, in electron volts, of the photon produced
when an electron in a hydrogen atom moves from the orbit with 𝒏 = 5 to the orbit
with 𝒏 = 2. Show your calculations.

4. How far from the nucleus in angstroms (1 𝑎𝑛𝑔𝑠𝑡𝑟𝑜𝑚 = 1 × 10 –10 𝑚) is the electron in
a hydrogen atom if it has an energy of – 8.72 × 10–20 𝐽?

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5. Consider a large number of hydrogen atoms with electrons randomly distributed in the 𝑛 =
1, 2, 3, 𝑎𝑛𝑑 4 orbits.
a) How many different wavelengths of light are emitted by these atoms as the electrons
fall into lower-energy orbitals?
b) Calculate the lowest and highest energies of light produced by the transitions described
in part (a).
c) Calculate the frequencies and wavelengths of the light produced by the transitions
described in part (b).
6. Show that the linear velocity of an electron in the nth orbit is given by; (4 marks)

1 𝑒2 1
𝑣=
4𝜋𝜀0 ℏ 𝑛

𝑚𝑒 𝑣𝑟 = 𝑛ℏ 

𝑛ℏ
𝑟= 
𝑚𝑒 𝑣

𝑛ℏ 𝑚𝑒 𝑣 2 𝑒2
𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦, 𝑟 = 𝑖𝑛𝑡𝑜 =  𝑎𝑛𝑑 𝑚𝑎𝑘𝑒 𝑣 𝑡ℎ𝑒 𝑠𝑢𝑏𝑗𝑒𝑐𝑡;
𝑚𝑒 𝑣 𝑟 4𝜋𝜀0 𝑟 2

𝑒 2 𝑚𝑒 𝑣 𝑒2
𝑚𝑒 𝑣 2 = ∙ ⟹𝑣= 
4𝜋𝜀0 𝑛ℏ 4𝜋𝜀0 ℏ𝑛

7. Calculate the linear velocity of an electron along the first orbit.

1 𝑒2 1 𝑁𝑚2 (1.602 𝑥 10−19 𝐶)2

𝑣=  = (8.991 𝑥 109 2 ) 𝑥 
4𝜋𝜀0 ℏ 𝑛 𝐶 (1.05 𝑥 10−34 Nm/s)
= 2.197 𝑥 106 𝑚/𝑠

8. Calculate the angular velocity 𝜔 and hence the linear frequency 𝐹.

𝑣 1 𝑒2 1 1 𝑒2 1 1
𝜔= 𝑏𝑢𝑡 𝑟 = 𝑎0 𝑛2 𝑎𝑛𝑑 𝑣 = ⟹𝜔= ∙
𝑟 4𝜋𝜀0 ℏ 𝑛 4𝜋𝜀0 ℏ 𝑛 𝑎0 𝑛2

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1 𝑒2 𝑘𝑒 2
𝜔= =
4𝜋𝜀0 ℏ𝑎0 𝑛3 ℏ𝑎0 𝑛3

𝜔 1 𝑒2 1 1 𝑒2
𝐿𝑖𝑛𝑒𝑎𝑟 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦, 𝐹 = = ∙ =
2𝜋 4𝜋𝜀0 ℏ𝑎0 𝑛3 2𝜋 8𝜋 2 𝜀0 ℏ𝑎0 𝑛3

9. Periodic time of the first orbit.

𝑚𝑒 𝑣 2 𝑒2
𝑚𝑒 𝑣𝑟 = 𝑛ℏ 𝑎𝑛𝑑 =
𝑟 4𝜋𝜀0 𝑟 2

2𝜋 ℏ𝑎0 𝑛3
𝑝𝑒𝑟𝑖𝑜𝑑𝑖𝑐 𝑇𝑖𝑚𝑒, 𝑇 = = 2𝜋 ∙
𝜔 𝑘𝑒 2

10. Define the terms ionizing energy and ionizing limit.

Ionizing energy; Energy needed to remove the electron from the atom.
Ionizing limit; Energy needed to remove the electron from first Bohr’s orbit.

11. If a hydrogen atom has its electron in the 𝑛 = 4 state, how much energy in eV is needed
to ionize it?
𝑧2 −18 )
12
𝐸𝑛 = −𝑘 = −(2.174 𝑥 10 = 1.359 𝑥 10−19 J
𝑛2 42
1.359 𝑥 10−19 J
𝐸𝑛 = = 0.850 𝑒𝑉
1.9 𝑥 10−19

12. Find the radius of a hydrogen atom in the 𝑛 = 2 state according to Bohr’s theory.

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𝑛2
𝑟= 𝑎 = 22 𝑥 (5.299 𝑥 10−11 𝑚) = 2.12 𝑥 10−10 𝑚
𝑧 0

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Lecture 4

4.0 De Broglie’s Hypothesis Applied to Atoms

In Bohr’s model, assumptions were made so that theory would agree with experiment. The theory
could not give the reason why the orbits were quantized and why there should be a stable ground
state. Louis de Broglie (1923 proposed that material particles, such as electrons, have a wave
nature; and that this hypothesis was confirmed by experiment several years later.

According to de Broglie, a particle of mass 𝒎 moving with a nonrelativistic speed 𝒗 would have
a wavelength given by;

ℎ
𝜆=
𝑚𝑣

Each electron orbit in an atom, he proposed, is actually a standing wave. The electron wave was a
circular standing wave that closes on itself.

If the wavelength of a wave does not close on itself, as in figure above, destructive interference
takes place as the wave travels around the loop, and the wave quickly dies out.

The only waves allowed are those for which the circumference of the circular orbit contains a
whole number of a wavelength;

2𝜋𝑟𝑛 = 𝑛𝜆

Substitute the wavelength in the de Broglie proposal;

ℎ 𝑛ℎ
2𝜋𝑟𝑛 = ⟹ 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚, 𝑚𝑣𝑟𝑛 = = 𝑛ℏ
𝑚𝑣 2𝜋
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This is just the quantum condition proposed in Bohr’s model. It is from this equation that the
discrete orbits and energy levels were derived.

This explanation of the quantized orbits and energy states in the Bohr model are due to the wave
nature of the electron, and only resonant “standing” waves can persist. This implies that the wave–
particle duality is at the root of atomic structure.

The circular wave represents the amplitude of the electron “matter wave,” and not the motion of
the electron.

Bohr’s theory worked well for hydrogen and for one-electron ions. But it did not prove successful
for multi-electron atoms. Bohr theory could not predict line spectra even for the next simplest
atom, helium. It could not explain why some emission lines are brighter than others, nor why some
lines are split into two or more closely spaced lines (“fine structure”).

Example

The velocity of an electron in the ground-state energy level of hydrogen is 2.2 𝑥 106 𝑚/𝑠 If the
electron's mass 𝑚 = 9.1 𝑥 10−31 𝑘𝑔.,what is the de Broglie wavelength of this electron?

Solution

ℎ 6.63 𝑥 10−34 𝑘𝑔 𝑚2 /𝑠
𝜆= = = 3.3 𝑥 10−10 𝑚
𝑚𝑣 (9.1 𝑥 10−31 𝑘𝑔)(2.2 𝑥 106 𝑚/𝑠)

The wavelength of this electron is on the same order of magnitude as the diameter of a hydrogen
atom ≈ 1 𝑥 10−10 𝑚.

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5.0 Fine Structure

Fine structure is the splitting of spectral lines in the absence of a magnetic field. A single spectral
appear as closely spaced doublets and is found in all atomic spectra.

It can be observed only by using equipment of very high resolution since the separation, in terms
of reciprocal wavelength, between adjacent components of a single spectral line is of the order of
10−4 times the separation between adjacent lines. What we had thought in Bohr model as a single
energy state of the hydrogen atom consists of several states which are very close together in energy.

Even without an external magnetic field, very precise measurements showed that spectral lines are
doublets – split into two.

Somerfield model
Bohr’s model couldn’t give predictions regarding the spectra of larger atoms and the fine structure
of the spectra lines. Arnold sommerfeld (1868-1951) extended the Bohr’s model to include
elliptical orbits instead of perfectly circular orbits. In this model, electrons travel in elliptical orbits
around the nucleus rather than in circular orbits.

According to Sommerfeld, the path of an electron around the nucleus may be both circular or
elliptical with the nucleus at one of its foci. When path is elliptical, then there are two axis – the
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major axis and the minor axis. When length of major and minor axis become equal then orbit is
circular.

The velocity of the electron moving in an elliptical orbit varies at different parts of the orbit. This
causes the relativistic variation in the mass of the moving electron hence variation in momentum
and energy of the electron. Contrary to Bohr’s model, Summerfield implied that angular
momentum was not common to all the electrons in same orbit.

Now, when elliptical orbits are permitted, one has to deal with two variable quantities.

1) The varying distance, 𝒓 of the electron from the nucleus.

2) The varying angular position, 𝜙 of the electron with respect to the nucleus i.e the azimuthal
angle 𝜙.

To deal with these two variables sommerfeld required two quantum numbers. Recall Bohr had
already introduced quantum number n. Sommerfeld introduced:

1) The principal quantum number 𝒏 of Bohr's theory, which determines the energy of the
electrons.
2) A new quantum number called orbital (or azimuthal) quantum number (𝒍) which has been
introduced to characterize the angular momentum in an orbit i.e., it determines the orbital
angular momentum of the electron. The values of 𝑙 range 0 ≤ 𝑙 ≥ (𝒏 − 1) in steps of unity.

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This orbital quantum number 𝑙 is useful in finding the possible elliptical orbits. The possible
elliptical orbits are such that:

𝑏 1 𝑏 1
= 𝑙+ 𝑜𝑟 𝑙 = −
𝑎 𝑛 𝑎 𝑛

where 𝑎 and 𝑏 are semi-major and semi-minor axes respectively of the ellipse.

According to Somerfield’s model, for any principal quantum number 𝒏, there are 𝒏 possible orbits
of varying eccentricities called sub-orbits or sub-shells. Out of 𝒏 subshells, one is circular and the
remaining i.e. (𝑛 − 1) orbits are elliptical in shape.

These possible sub-orbits possess slightly different energies because of the relativistic variation of
the electron mass.

Consider the first energy level (𝑛 = 1).

When 𝑛 = 1, from the range 0 ≤ 𝑙 ≥ (𝒏 − 1) then 𝑙 = 0 implying that in this energy level,
there is only one orbit or sub-shell for the electron.

𝑏 1
𝐹𝑟𝑜𝑚 𝑙 = − 𝑎𝑛𝑑 𝑙 = 0 ⟹ 𝑏 = 𝑎
𝑎 𝑛

Also, 𝑙 = 0 then 𝑎 = 𝑏, the two axes of the ellipse are equal. As a result of this, the orbit
corresponding to 𝑛 = 1 is circular. This subshell is designated as 𝑠 sub-shell. Since, this sub-shell
belongs to 𝑛 = 1, it is designated as 1𝑠.

Similarly, for the second energy level 𝑛 = 2, there are two permissible sub-shells for the electrons.
For 𝑛 = 2, 𝑙 can take two values; 0 and 1.

When 𝑛 = 2 𝑎𝑛𝑑 𝑙 = 0.
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𝑏/𝑎 = 0 + 1/2 = 1/2

𝑏 = 𝑎/2
This subshell corresponding to l = 0 is elliptical in shape and is designated as 2𝒔.
when 𝑛 = 2, 𝑙 = 1.
𝑏/𝑎 = 1 + 1/2 = 2/2 = 1
𝑏=𝑎
This sub-shell corresponding to l = 1 is circular in shape and is designated as 2p.

For 𝑛 = 3, 𝑙 has three values 0, 1 and 2, i.e. there are three permissible sub-shells for the electrons.

When 𝑛 = 3, 𝑙 = 0.

𝑏/𝑎 = (0 + 1)/3 = 1/3 = 1 𝑜𝑟 𝑏 = 𝑎/3

When 𝑛 = 3, 𝑙 = 1.

𝑏/𝑎 = (1 + 1)/3 = 2/3 = 1 𝑜𝑟 𝑏 = 2𝑎/3

and when 𝑛 = 3, 𝑙 = 2.

𝑏/𝑎 = (2 + 1)/3 = 3/3 = 1 𝑜𝑟 𝑏 = 𝑎

The sub-shells corresponding to 𝑙 = 0, 1 and 2 are designated as 3𝒔, 3𝒑 and 3𝒅 respectively. The
circular shell is designated as 3𝒅 and the other two are elliptical in shape.

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It is common practice to assign letters to 𝑙-values as given below:

Orbital quantum number 𝑙 = 0, 1, 2, 3, 4, …

electron state: s, p, d, f, g, …

Hence, electrons in the l = 0, 1, 2, 3 and states are said to be in the s, p, d, f…

All states with the same principal quantum number 𝑛 are said to form a shell. Shells are identified
by the letters K, L, M, . . . , which designate the states for which 𝑛 = 1, 2, 3, . . ..

Likewise, the states with given values of 𝑛 and 𝑙 are said to form a subshell. The letters s, p, d, f,
g, . . . are used to designate the states for which 𝑙 = 0, 1, 2, 3, 4, . .. .

Another modification of the Bohr theory arose when it was discovered that the spectral lines of a
gas are split into several closely spaced lines when the gas is placed in a strong magnetic field.
(This is called the Zeeman effect, after its discoverer.)

Figure below shows a single spectral line being split into three closely spaced lines.

A single line (A) can split into three separate lines (B) in a

magnetic field.

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This indicates that the energy of an electron is slightly modified when the atom is immersed in a
magnetic field. In order to explain this observation, a new quantum number, 𝑚𝑙 called the orbital
magnetic quantum number, was introduced.

Drawbacks

1) Though Sommerfeld's modification gave a theoretical background of the fine structure of

spectral lines of hydrogen, it could not predict the correct number of observed fine structure of
these lines.
2) It could not explain the distribution and arrangement of electrons in atoms.
3) Sommerfeld's model was unable to explain the spectra of alkali metals such as sodium,
potassium etc.
4) It could not explain Zeeman and Stark effect.
5) This model does not give any explanation for the intensities of the spectral lines.

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Lecture 5

6.0 Zeeman’s Effect

The Zeeman effect is a magnetic optical phenomenon in which spectral lines are affected by an
applied magnetic field and split into several components. The Zeeman effect, named after the
Dutch physicist Pieter Zeeman, is the effect of splitting of a spectral line into several components
in the presence of a static magnetic field.

Pieter Zeeman (1865–1943) discovered spectral lines were split into two or more separate emission
lines by an external magnetic field. Some lines split into three lines, some into five, and so on. The
extent of the split lines are separated is proportional to the applied field strength ⃗𝑩
⃗ , indicating an
interaction with a moving charge. The quantized energy of an electron is affected by an external
magnetic field, causing the orbit to have several discrete energies instead of one.

Two spectral lines with no external magnetic

field.

The lines split when the field is applied.

The space in splitting is greater when a stronger

field is applied.

Theoretically, this is explained by recognizing that an electron has an orbital magnetic moment.
The electron experience Lorentz force when placed in the presence of external magnetic field. The
motion of electron in atom is assumed to be harmonic with a specific angular frequency and
energy. Application of magnetic field may increase or reduce the angular frequency hence the
different splitting of the energy levels.

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Normal Zeeman effect and anomalous Zeeman effect

A normal Zeeman effect is observed when a spectral line of an atom splits into three lines under a
magnetic field.

An anomalous Zeeman effect is observed if the spectral line splits into more than three lines. When
an atom is placed in a magnetic field, each of its fine structure lines further splits into a series of
equidistant lines with a spacing proportional to the magnetic field strength.

Stark Effect
The Stark effect is the shifting and splitting of spectral lines of atoms due to the presence of an
external electric field. The effect is named after the German physicist Johannes Stark, who
discovered it in 1913.

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7.0 Magnetic Properties of Electron

An electron revolving around the nucleus in an orbit produces a magnetic field which interacts
with other magnetic fields when the atom is placed in the presence of an external magnetic field.

From the Bohr’s model of the hydrogen atom, the electron moves in a circular orbit around the
proton.

The electron (charge) passes by a particular point on the loop in a certain time, so we can calculate
a current, I.

𝑄 𝑄
𝐶𝑢𝑟𝑟𝑒𝑛𝑡, 𝐼 = = 𝑤ℎ𝑒𝑟𝑒 𝑇 𝑖𝑠 𝑡ℎ𝑒 𝑝𝑒𝑟𝑖𝑜𝑑𝑖𝑐 𝑡𝑖𝑚𝑒.
𝑡 𝑇

From magnetism we know that current-carrying wire produces magnetic fields. A hydrogen atom
is therefore analogous to current flowing through a circular wire. In order to measure of the
strength of the magnetic field produced by the orbiting electron, we evaluate on orbital magnetic
dipole moment 𝜇.

Externally provided magnetic field B cause the turning effect on the circular orbit of the electron.
Orbital magnetic dipole moment is a measure of magnetic field produced by the orbiting electron.
This is indirect measuring of the magnetic field due to the revolving of charged electron in the
closed orbit. Instead we measure the turning effect on the electron circuit loop known as magnetic
moment – a measure of magnetic strength and orientation for any object that produce a magnetic
field e.g. loops of electric current.

The magnitude of the orbital magnetic dipole moment (simply known as magnetic moment, 𝜇) for
a current loop is given as:

𝑀𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑚𝑜𝑚𝑒𝑛𝑡, 𝜇 = 𝑐𝑢𝑟𝑟𝑒𝑛𝑡, 𝐼 𝑥 𝑒𝑛𝑐𝑙𝑜𝑠𝑒𝑑 𝑎𝑟𝑒𝑎, 𝐴

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where I is the current and A is the enclosed area. The SI unit is ampere square meter (𝐴 𝑚2 ).

The current, I associated with an electron in orbit about a proton in a hydrogen atom is:

𝑄 𝑒
𝐶𝑢𝑟𝑟𝑒𝑛𝑡, 𝐼 = =
𝑡 𝑇

Where e is the magnitude of the electron charge and T is its orbital period. If we assume that the
electron travels in a perfectly circular orbit, the orbital period is:

2𝜋𝑟
𝑇=
𝑣

Where r is the radius of the orbit and v is the linear speed of the electron in its orbit. Given that the
area of a circle is 𝜋𝑟 2 , the absolute magnetic moment is:

𝑒 𝑒𝑣𝑟
𝜇 = 𝐼𝐴 = ∙ (𝜋𝑟 2 ) =
2𝜋𝑟 2
( 𝑣 )

Magnetic moment in terms of angular momentum

The magnitude of the orbital angular momentum, |L| is:

⃗ | = |𝑟|𝑥|𝑃⃗| = 𝑟𝑝 sin 𝜃 = 𝑟𝑝 = 𝑟𝑚𝑣

𝐿 = |𝐿

𝐿
𝑣𝑟 =
𝑚

Therefore; to express the magnetic momentum 𝜇 in terms of the orbital angular momentum, L.

𝑒 𝑒 𝐿 𝑒
𝜇= (𝑣𝑟) = = −( )𝐿⃗
2 2𝑚 2𝑚

The negative sign appears because the electron has a negative charge.

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Notice that the direction of the magnetic moment of the electron is antiparallel to the orbital angular
momentum.

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Lecture 6

8.0 Quantum Atomic Model

A major problem with Bohr's model was that it treated electrons as particles that existed in
precisely-defined orbits. Based on de Broglie's idea that particles could exhibit wavelike behavior,
Austrian physicist Erwin Schrödinger proposed that the behavior of electrons within atoms could
be explained by treating them mathematically as matter waves. This model, which is the basis of
the modern understanding of the atom, is known as the quantum mechanical or wave mechanical
model.

The fact that there are only certain allowable states or energies that an electron in an atom can have
is similar to a standing wave. This lead to the limitation that only certain wavelengths are allowed
for any standing wave. As such, the vibrations are quantized.

Schrödinger's Equation
Schrödinger formulated a model of the atom that assumed the electrons could be treated like matter
waves. He formulated the basic form of Schrödinger's wave equation is as follows:

̂ 𝜓 = 𝐸𝜓
H

Where ψ is called a wave function which is proportional to the amplitude of the electron matter
̂ , with, hat, on top is known as the Hamiltonian operator; and E is the binding
wave at that point.; H
energy of the electron. Solving Schrödinger's equation yields multiple wave functions as solutions,
each with an allowed value for E.

Angular operator 𝐿̂ operated on wave function 𝜓 to obtain the magnitude of the angular momentum
L.

L̂2 𝜓 = 𝐿2 𝜓 ⟹ 𝐿 = √𝑙(𝑙 + 1) ℏ

Where l is the orbital quantum number.

𝑅𝑒𝑐𝑎𝑙𝑙 𝑡ℎ𝑒 𝑣𝑎𝑙𝑢𝑒𝑠 𝑜𝑓 𝑙 = 0, 1, 2, … (𝑛 − 1)

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The function 𝜓2 squared is often called the probability density. It gives the relative probabilities
of finding an electron in a given region in space. The idea of well-defined orbits was replaced by
electron “clouds”. The focus moved from an individual electron to a “cloud” where electron can
be found.

Due to the Heisenberg uncertainty principle, it is impossible to know for a given electron both its
position and its energy.

Quantum Numbers and Rules

Quantum numbers are used to express the allowed values of quantized entities. Physical quantities
that are quantized include; radius, energy and angular momentum.

Quantized Energy Levels, En

The energy states (levels) of bound (fixed) systems are quantized, because the particle wavelength
can fit into the bounds of the system in only certain ways. This was elaborated for the hydrogen
atom, for which the allowed energies are expressed as 𝐸 = 1/𝑛2 , where 𝑛 = 1, 2, 3, . . .. We define
𝒏 the principal quantum number that labels the basic energy states of a system. The lowest-energy
state has 𝒏 = 𝟏, the first excited state has 𝒏 = 𝟐, and so on. Thus the allowed values for the
principal quantum number are; 𝑛 = 1, 2, 3, … . The energy of the system, such as the hydrogen
atom, can be expressed as some function of 𝒏.

Angular momentum

The magnitude of angular momentum, 𝑳 is quantized was first recognized by Bohr and later
established that 𝑳 can have only the values:

𝐿 = √𝑙(𝑙 + 1) ℏ 𝑤ℎ𝑒𝑟𝑒 𝑙 = 0, 1, 2, … , (𝑛 − 1)

Considering angular momentum is a vector in space, we can resolve to obtain the z-component
along the direction of the applied magnetic field. The magnitude of 𝐿𝑧 depend on the direction.

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⃗
𝑩

Example

Given the value of 𝑛 = 4, the values of 𝑙 = 0, 1, 2 𝑎𝑛𝑑 3.

for 𝑙 = 2, 𝐿 = √2(2 + 1) ℏ = √6 ℎ⁄2𝜋 = 0.39 ℎ = 2.58 𝑥 10−34 J. s

From the Zeeman effect, the direction (orientation) of angular momentum is also quantized in
space. The angular momentum component 𝐿𝑧 along magnetic direction, usually called the z-axis,
can have only certain values. The allowed values of 𝐿𝑧 are:

𝐿𝑧 = 𝑚𝑙 ℏ 𝑤ℎ𝑒𝑟𝑒 𝑚𝑙 = −𝑙, −𝑙 + 1, … , −1, 0, 1, … 𝑙 − 1, 𝑙

Where 𝑚𝑙 is the angular momentum projection quantum number. The rule in parentheses for the

values of 𝑚𝑙 is that it can range from −𝑙 to 𝑙 in steps of one.

𝑚𝑙 = −𝑙, −𝑙 + 1, … , 0, … , 𝑙 − 1, 𝑙

For 𝑙 = 2, then 𝑚𝑙 can have the five values –2, –1, 0, 1, 2. Each 𝑚𝑙 corresponds to a different
energy in the presence of a magnetic field, so that they are related to the splitting of spectral lines
into discrete parts. If the z-component of angular momentum can have only certain values, then
the angular momentum can have only certain directions – quantized in space.

For l=1, for which 𝑚𝑙 = −1, 0, 1. The direction of 𝐿 is quantized in the sense that it can have only
certain angles relative to the z-axis.

Example

Calculate the angles that the angular momentum vector 𝐿 can make with the z-axis for 𝑙 = 1, as
illustrated in the figure.

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We calculate the modulus of vector L.

𝐿 = √𝑙(𝑙 + 1) ℏ = √2 ℏ

ℏ 𝑚𝑙 = +1
𝐿𝑧 = 𝑚𝑙 ℏ = { 0 𝑚𝑙 = 0
−ℎ 𝑚𝑙 = −1

𝐿𝑧 𝐿𝑧
cos 𝜃 = ⟹ 𝜃 = cos −1 ( )
𝐿 𝐿

ℏ
𝜃1 = cos −1 ( ) = cos −1 0.707 = 45°
√2 ℏ

0
𝜃2 = cos−1 ( ) = cos −1 0 = 90°
√2 ℏ

−ℏ
𝜃3 = cos−1 ( ) = cos −1 − 0.707 = 135°
√2 ℏ

Intrinsic Spin Angular Momentum

There are two quantum numbers associated with intrinsic angular momentum of the electron. They
were first discovered for electrons in conjunction with fine structure in atomic spectra. Only one
magnitude of intrinsic spin is allowed for a given type of particle. Additionally, the direction of
the spin is also quantized. It has been found that the magnitude of the intrinsic (internal) spin
angular momentum, S, of an electron is given by:

1
𝑆 = √𝑠(𝑠 + 1) ℏ 𝑤ℎ𝑒𝑟𝑒 𝑠 = .
2

Where s is defined to be the spin quantum number.

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The direction of intrinsic spin is quantized, just as is the direction of orbital angular momentum.
The direction of spin angular momentum along one direction in space, again called the z-axis, can
have only the values;

1 1
𝑆𝑧 = 𝑚𝑠 ℏ 𝑤ℎ𝑒𝑟𝑒 𝑚𝑠 = − , +
2 2

𝑆𝑧 is the z-component of spin angular momentum and 𝑚𝑠 is the spin projection quantum number.

For electrons, 𝒔 can only be 1/2, and 𝒎𝒔 can be either +1/2 or –1/2. Spin projection 𝑚𝑠 = +1/2
is referred to as spin up, whereas 𝑚𝑠 = −1/2 is called spin down.

Intrinsic Spin

Intrinsic spin is a characteristic of all subatomic particles. For some particles s is half-integral,
whereas for others s is integral—there are crucial differences between half-integral spin particles
and integral spin particles. Protons and neutrons, like electrons, have s=1/2, whereas photons
have s=1, and other particles called pions have s=0, and so on.

To summarize, the state (energy level) of a system (electron), such as the precise nature of an
electron in an atom, is determined by its particular quantum numbers. These are expressed in the
form (𝑛, 𝑙, 𝑚𝑙 , 𝑚𝑠 ).

For electrons in atoms, the principal quantum number can have the values 𝑛 = 1, 2, 3, . . .. Once 𝑛
is known, the values of the angular momentum quantum number are limited to 𝑙 = 1, 2, . . , 𝑛 − 1.
For a given value of 𝑙, the angular momentum projection quantum number can have only the values
{𝑚𝑙 = −𝑙, −𝑙 + 1, … , −1, 0, 1, … 𝑙 − 1, 𝑙. The spin projection quantum number can have two
1 1
values, 𝑚𝑠 = − 2 , + 2.

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Degeneracy

An energy level is said to be degenerate if it can be described by more than one quantum state.

Questions

1. Define the quantum numbers 𝑛, 𝑙, 𝑚𝑙 , 𝑠, 𝑚𝑠 .

2. For a given value of 𝑛, what are the allowed values of 𝑙?
3. For a given value of 𝑙, what are the allowed values of 𝑚𝑙 ?
4. What are the allowed values of 𝑚𝑙 for a given value of 𝑛? Give an example in each case.
5. List all the possible values of s and 𝑚𝑠 for an electron.
6. If an atom has an electron in the 𝑛 = 5 state with 𝑚𝑙 = 3, what are the possible values of 𝑙?
𝑙 = 4, 3 are possible since 𝑙 < 𝑛 and mid 𝑙 ≥ |𝑚𝑙 |.

7. An atom has an electron with 𝑚𝑙 = 2. What is the smallest value of 𝑛 for this electron?
8. What are the possible values of 𝑚𝑙 for an electron in the 𝑛 = 4 state?
𝑛 = 4 ⇒ 𝑙 = 3, 2, 1, 0 ⇒ 𝑚𝑙 = ±3, ±2, ±1 and 0 are possible.

9. What, if any, constraints does a value of 𝑚𝑙 = 1 place on the other quantum numbers for an
electron in an atom?
10) a) Calculate the magnitude of the angular momentum for an 𝑙 = 1 electron.
b) Compare your answer to the value Bohr proposed for the 𝑛 = 1 state.
11) a) What is the magnitude of the angular momentum for an 𝑙 = 1 electron?
b) Calculate the magnitude of the electron’s spin angular momentum.

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c) What is the ratio of these angular momenta?

12) a) How many angles can 𝑳 make with the z-axis for an 𝒍 = 𝟐 electron?
b) Calculate the value of the smallest angle.
c) What angles can the spin 𝑺 of an electron make with the z-axis?

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Lecture 7

9.0 Vector Atomic Model

This is a model that describe an atom in terms of total angular momentum. Angular momentum is
a vector quantity with both magnitude and direction. We have two angular momentum associated
with the electron; orbital angular momentum L and the spin angular momentum. The total angular
momentum of an atom result from the combination of the orbital and spin angular momenta of its
electrons. Angular momentum is a vector quantity, so we can represent the total angular
momentum by means of a vector 𝑱 obtained by the addition of orbital angular momentum 𝑳 and
spin angular momentum S vectors.

𝐽 =𝐿+𝑆

The orbital angular momentum 𝑳 of electron comes from the revolution of electron in certain
stationary orbits around nucleus whereas spin angular momentum 𝑺 of electron is inherent and it
comes from the revolution of electron around itself.

The orbital angular momentum of electron is 𝐿 = √(𝑙(𝑙 + 1)) ℎ/2 𝜋, where the values of 𝑙 are 0
(s), 1 (p), 2 (d), ………

For example, for ℓ = 2, we see that:

𝐿 = ℏ√𝑙(𝑙 + 1) = (1.055 𝑥 10−34 )√2(2 + 1) = (1.055 𝑥 10−34 )√6 = 2.58 𝑥 10−34 𝐽𝑠

Both the angular momentums are quantized. The quantization refers to the projection of 𝑳 along
the Z-direction (𝐿𝑧 ) which have discrete values only. The orbital magnetic quantum number 𝑚𝑙
gives the direction of L and tells the possible components of L in the Z-direction (the field
direction).

𝐿𝑧 = 𝑚𝑙 ℏ 𝑤ℎ𝑒𝑟𝑒 𝑚𝑙 = 𝑙, 𝑙 − 1, 𝑙 − 2, … , … , −𝑙

The phenomenon of quantization of L in the direction of magnetic field B is commonly known as

space quantization.

The possible values of 𝑚𝑙 for 𝑙 = 2 can be −2, −1, 0, 1, 2 hence 𝐿𝑧 = 𝑚𝑙 ℏ = −2ℏ, – ℏ, 0, ℏ, 2ℏ.
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The L can be visualized as a vector lying on the surface of a cone.

The spin angular momentum of electron is 𝑆 = √𝑠(𝑠 + 1)) ℎ/2 𝜋, where 𝑠 takes the value 1/2.

1 1 √3
𝑆 = √ ( + 1) ℏ = ℏ
2 2 2

Similarly, the spin angular momentum S is also space quantized.

1 1
𝑆𝑧 = 𝑚𝑠 ℏ 𝑤ℎ𝑒𝑟𝑒 𝑚𝑠 = +𝑠, −𝑆 = + ,−
2 2

1
𝑆𝑧 = ± ℏ
2

Geometrically, it can also be viewed as a cone without the circular base.

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The total angular momentum of one electron atom 𝐽 is a vector sum of 𝐿 and 𝑆.

⃗ + 𝑆
J= 𝐿

The modulus of the total angular momentum J;

|J| = √𝑗(𝑗 + 1)) ℏ

Similarly, the total angular momentum J is also space quantized.

Jz = 𝑚𝑗 ℏ 𝑤ℎ𝑒𝑟𝑒 𝑚𝑗 = +𝑗, 𝑗 − 1, 𝑗 − 2, … , … , −𝑗

The vector J is space quantized w.r.t. external field B i.e. it can have only (2j+1) number of discrete
orientations w.r.t. external field B.

This vector atom model of an atom successfully explains the fine structure of spectral lines and
Zeeman effect (normal and anomalous).

Worked Example

Given orbital angular momentum number 𝑙 = 1 calculate;

i) The possible values of total angular momentum number 𝑗.

ii) The modulus of the angular momentum J.

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Solution

For any given value of 𝑙 there are two values of 𝑗; 𝑗1 = 𝑙 + 1⁄2 and 𝑗2 = 𝑙 − 1⁄2

𝑗1 = 1 + 1⁄2 = 3⁄2 𝑎𝑛𝑑 𝑗2 = 1 − 1⁄2 = 1⁄2

√3
|J| = √𝑗(𝑗 + 1)) ℏ 𝑤ℎ𝑒𝑛 𝑗 = 1⁄2 𝑡ℎ𝑒𝑛 |J| = √1⁄2 (1⁄2 + 1)) ℏ = ℏ
2

√15
𝑤ℎ𝑒𝑛 𝑗 = 3⁄2 𝑡ℎ𝑒𝑛 |J| = √3⁄2 (3⁄2 + 1)) ℏ = ℏ
2

From the above example, the kind of combination is visualized in terms of a vector model of
angular momentum.

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Example

What are the possible orientations of J for the 𝑗 = 3⁄2 and 𝑗 = 1⁄2 states that correspond to 𝑙 =
1?

Solution

For the 𝑗 = 3⁄2, 𝑚𝑗 = −𝑗, −𝑗 + 1, … , 𝑗 − 1, 𝑗 ⟹ − 3⁄2 , − 1⁄2 , 1⁄2 , 3⁄2

For the 𝑗 = 1⁄2, 𝑚𝑗 = −𝑗, −𝑗 + 1, … , 𝑗 − 1, 𝑗 ⟹ − − 1⁄2 , − 1⁄2

Example

Enumerate the possible values of j and mj for the states in which 𝑙 = 1 and 𝑠 = 1/2 and draw
the associated vector diagrams.

Solution

j = l+ s = 1 + ½ = 3/2

mj = -j, -j +1,…, j 𝑚𝑗 = − 3⁄2 , − 1⁄2 , 1⁄2 , 3⁄2

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Coupling Schemes
The term "coupling" in this context means the vector superposition of angular momenta, that is,
magnitudes and directions are added. For one-electron atoms (i.e. hydrogen), there is only one set
of cones for the orbiting electron. For multi-electron atoms, there are many states, due to the
increasing number of electrons. The angular momenta of all electrons in the atom add vectorially.

An electronic state of an atom is obtained by the way the orbital and spin angular momenta of the
different electrons are coupled together. There are two descriptions for the coupling of angular
momentum. One is called j-j coupling, and the other is called L-S coupling. The j-j coupling
scheme is used for heavy elements (𝑧 > 40), and the L-S coupling scheme is used for the lighter
elements.

L-S Coupling
L-S coupling also is called R-S or Russell-Saunders coupling. In L-S coupling, the orbital and spin
angular momenta of all the electrons are combined separately;

𝐿 = ∑ 𝐿𝑖 𝑎𝑛𝑑 𝑆 = ∑ 𝑆𝑖
𝑖 𝑖

A group II element with two active electrons each having spin 𝑠1 = +½ and 𝑠2 = + ½. The
resultant spin 𝑆 = 𝑠1 ± 𝑠2 ⟹ 𝑆 = ½ + ½ 𝑜𝑟 𝑆 = ½ − ½ = 0 and therefore s values are
𝑆 = 1, 0 (vectorially).

Consider an atom with 𝑙1 = 1, 𝑙2 = 0. Then;

𝐿 = ∑ 𝐿𝑖 = 1 + 0 = 1
𝑖

The total angular momentum vector J is the sum of the total orbital angular momentum vector and
the total spin angular momentum vector.

J = 𝐿 + 𝑆; 𝑤ℎ𝑒𝑟𝑒 𝑡ℎ𝑒 𝑠𝑡𝑎𝑡𝑒𝑠 𝑎𝑟𝑒 𝑙 + 𝑠, 𝑙 + 𝑠 − 1, … , 𝑙 − 𝑠

Given 𝐿 = 1, 𝑆 = 0 𝑜𝑟 1.

When 𝐿 = 1, 𝑆 = 0, 𝑡ℎ𝑒𝑛 𝐽 = 1, giving only one energy level.

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When 𝐿 = 1, 𝑆 = 1: there are three possible ways of combining L and S.

J = 𝐿 + 𝑆; 𝑡ℎ𝑒 𝑠𝑡𝑎𝑡𝑒𝑠 𝑎𝑟𝑒 𝑙 + 𝑠, 𝑙 + 𝑠 − 1, … , 𝑙 − 𝑠

Giving 𝐽 = 2, 1, 0; There are three orientations with slightly different energies of magnetic
interactions, leading to three separate energy levels.

The multiplicity, which is the number of levels into which each term splits, is given by (2S+ 1).

In group III, there are three active electrons with spin quantum number s1 , s2 , s3 each equal to
1⁄ . These can be oriented so that they are all parallel () giving 𝑆 = 1⁄ + 1⁄ + 1⁄ =
2 2 2 2
3⁄ .
2

If 𝐿 = 2, 𝑆 = 3/2 then 𝐽 = 𝐿 + 𝑆 𝑤ℎ𝑒𝑟𝑒 𝑙 + 𝑠, 𝑙 + 𝑠 − 1, … , 𝑙 − 𝑠.

Then 𝐿 + 𝑆 = 7⁄2 , 5⁄2 , 3⁄2 , 1⁄2: Giving rise to four energy levels.

With one reversed () giving 𝑆 = 1⁄2 + 1⁄2 − 1⁄2 = 1⁄2

If 𝐿 = 2, 𝑆 = 1/2, then 𝐽 = 𝐿 + 𝑆 to 𝐿 − 𝑆 = 5/2, 3/2: giving rise to two energy levels.

L-S coupling holds for a large number of elements, including all the light elements.

Example

Given two quantum number 𝑙 = 2 and 𝑙 = 3 what are the possible values of total angular
momentum number j.

Solution

For any value of l there are two values of j.

1 1
𝑗=𝑙+ 𝑎𝑛𝑑 𝑗 = 𝑙 −
2 2
1 1 5 3
𝑙 = 2 ⟹ 𝑗 = 2+ ,2− ⟹ ,
2 2 2 2
1 1 7 5
𝑙 = 3 ⟹ 𝑗 = 3+ ,3− ⟹ ,
2 2 2 2

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Example

Determine the number of energy levels when the angular momentum is combined in LS coupling
for an atom with two electrons in 2s and 2p states respectively.

Solution

For electron in 2s states; 𝑠 = 1⁄2 and 𝑙 = 0.

For electron in 2p states; 𝑠 = 1⁄2 and 𝑙 = 1.

In LS coupling; 𝐿 = ∑𝑖 𝐿𝑖 = 0 + 1 = 1 and 𝑆 = ∑𝑖 𝑆𝑖 = 1⁄2 + 1⁄2 = 1

𝐽 = 𝐿 + 𝑆; 2,1,0 𝑡ℎ𝑒𝑠𝑒 𝑎𝑟𝑒 3 𝑠𝑡𝑎𝑡𝑒𝑠.

For electron in 2s states; 𝑠 = 1⁄2 and 𝑙 = 0.

For electron in 2p states; 𝑠 = − 1⁄2 and 𝑙 = 1.

In LS coupling; 𝐿 = ∑𝑖 𝐿𝑖 = 0 + 1 = 1 and 𝑆 = ∑𝑖 𝑆𝑖 = 1⁄2 − 1⁄2 = 0

𝐽 = 𝐿 + 𝑆; 1 𝑡ℎ𝑖𝑠 𝑖𝑠 𝑜𝑛𝑒 𝑠𝑡𝑎𝑡𝑒.

Total number of states; 4 states.

JJ Coupling
It is applied when multiple electrons contribute to the net angular momentum.

In atoms with bigger nuclear charges, spin-orbit interactions are frequently as large as or larger
than spin-spin interactions or orbit-orbit interactions. In this situation, each orbital angular
momentum ℓ𝑖 tends to combine with the corresponding individual spin angular momentum 𝑠𝑖 ,
originating an individual total angular momentum 𝑗𝑖 . These then couple up to form the total angular
momentum J.

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𝐽 = ∑ 𝑗𝑖 = ∑(𝑗𝑖 + 𝑠𝑖 )
𝑖 𝑖

Thus we have for each separate electron, 𝑗1 = 𝑙1 + 𝑠1 , 𝑗2 = 𝑙2 + 𝑠2 , .......... and

𝐽 = 𝑗1 + 𝑗2 + 𝑗3 + . . ..

Pure j-j coupling is rarely found but many of the heavier elements have spectra which can only be
interpreted in terms of a coupling intermediate between L-S and j-j.

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Lecture 8

10.0 Bohr Magneton

An electron revolving around the nucleus along the orbit behaves like a magnet. It generates a
magnetic field which interact with any other magnetic field hence causing the Zeeman effect.
The magnetic moment (µ) is a vector quantity used to measure the tendency of an object to
interact with an external magnetic field.

Magnetic moment is given;

𝑒𝑣𝑟
𝜇 =
2

Magnetic moment is related to orbital angular momentum as;

𝑒 𝑒 𝐿 𝑒
𝜇= (𝑣𝑟) = = −( )𝐿⃗
2 2𝑚 2𝑚

𝑒
Where (2𝑚) is the Gyromagnetic ratio i.e.

𝑒 𝜇
( )=
2𝑚 ⃗
𝐿

From Quantum model of an atom; the magnitude of angular momentum, L is related to orbital
quantum number, l by:

𝐿 = √𝑙(𝑙 + 1) ℏ

Expressing magnetic moment in terms of orbital quantum number l,

𝑒 𝑒ℏ
𝜇= √𝑙(𝑙 + 1) ℏ = √𝑙(𝑙 + 1) = 𝜇𝐵 √𝑙(𝑙 + 1)
2𝑚 2𝑚

𝑒ℏ
Where a constant, 𝜇𝐵 = 2𝑚 is called the 𝐁𝐨𝐡𝐫 𝐦𝐚𝐠𝐧𝐞𝐭𝐨𝐧. This is the minimum magnetic

moment when 𝑙 = 0 and √𝑙(𝑙 + 1) = 1.

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𝐽𝑜𝑢𝑙𝑒𝑠
The value of called the Bohr magneton 𝜇𝐵 = 9.3 𝑥 10−24 (𝐽/𝑇)
𝑇𝑒𝑠𝑙𝑎

Quantization of the magnetic moment, 𝜇𝐵 is the result of quantization of the orbital angular
momentum.

Again from quantum model, the z – component of angular momentum;

𝐿𝑧 = 𝑚𝑙 ℏ

We found that in quantum model, the angular momentum has different orientation depending on
the angular momentum projection quantum number 𝑚𝑙 .

Where, 𝑚𝑙 is the angular momentum projection quantum number (or magnetic orbital quantum
number), which has the value 𝑚 = −𝑙, − 𝑙 + 1, … , 0, … , 𝑙 − 1, 𝑙.

The Z-component of magnetic moment, 𝜇𝑧 :

𝑒 𝑒
𝜇𝑧 = − ( ) 𝐿𝑧 = − ( ) 𝑚𝑙 ℏ = − 𝜇𝐵 𝑚𝑙
2𝑚𝑒 2𝑚𝑒

Examples

Considering the spin of an electron to be zero calculate the magnitude of the orbital dipole
magnetic moment 𝜇 and 𝜇𝑧 of an electron in the hydrogen atom that is;

i) s state.
ii) p state.
iii) d state.

Solution

𝜇 = 𝜇𝐵 √𝑙(𝑙 + 1)

𝐹𝑜𝑟 𝑠 𝑠𝑡𝑎𝑡𝑒, 𝑙 = 0 ⟹ 𝜇 = 0

(𝑁𝑜 𝑚𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑚𝑜𝑚𝑒𝑛𝑡 ⟹ 𝑇ℎ𝑒 𝑚𝑜𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑑𝑜𝑒𝑠 𝑛𝑜𝑡 𝑝𝑟𝑜𝑑𝑢𝑐𝑒 𝑚𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑓𝑖𝑒𝑙𝑑)

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𝜇 = 𝜇𝐵 √𝑙(𝑙 + 1)

𝐹𝑜𝑟 𝑝 𝑠𝑡𝑎𝑡𝑒, 𝑙 = 1 ⟹ 𝜇 = 𝜇𝐵 √1(1 + 1) = √2 𝜇𝐵 = √2 𝑥 (9.3 𝑥 10−24 )

𝜇 = 1.3 𝑥 10−23 𝐽/𝑇

𝜇𝑧 = − 𝜇𝐵 𝑚 𝑤ℎ𝑒𝑟𝑒 𝑚 = (−1,0,1) ⟹ 𝜇𝑧 = − 𝜇𝐵 , 0, 𝜇𝐵

The magnetic moment has three possible values of the z-component.

Magnetic moment can point in three different polar directions.

𝜇 = 𝜇𝐵 √𝑙(𝑙 + 1)

𝐹𝑜𝑟 𝑝 𝑠𝑡𝑎𝑡𝑒, 𝑙 = 2 ⟹ 𝜇 = 𝜇𝐵 √2(2 + 1) = √6 𝜇𝐵 = √6 𝑥 (9.3 𝑥 10−24 )

𝜇 = 2.28 𝑥 10−23 𝐽/𝑇

𝜇𝑧 = − 𝜇𝐵 𝑚 𝑤ℎ𝑒𝑟𝑒 𝑚 = (−2, −1,0,1, 2) ⟹ 𝜇𝑧 = −2 𝜇𝐵 , − 𝜇𝐵 , 0, 𝜇𝐵 , 2 𝜇𝐵

There are five possible values for the z-component for 𝜇𝑧 .

g-factor (also called g value or dimensionless magnetic moment)

There was a slight difference between observed magnetic moment and the theoretical for electrons
whose spin momentum was not equal to zero. This lead Alfred Landé (1921) to introduce a g-
factor when attempting to account for the Zeeman effect.

𝑒
𝜇 = −𝑔 ( ⃗
)𝐿
2𝑚

Where g was to be determined experimentally.

Importance of the g-Factor

The value of Lande g factor can be used to distinguish between the normal and anomalous Zeeman
effect. Lande g factor indicates the kind of Zeeman effect taking place
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Spectral emission lines exhibiting normal Zeeman effect involve transition between Energy states
that have zero spin angular momentum. And the orbital and the total angular momentum are
identical. And the lande g factor for both the energy levels 𝑔 = 1.

Spectral lines that exhibit anomalous Zeeman effect involve Energy levels having non zero spin
angular momentum. And because of that, the lande g factor for the two Energy levels are different
and anomalous Zeeman effect is observed.

Electron g factors

There are three magnetic moments associated with an electron:

a) one from its spin angular momentum, S

b) one from its orbital angular momentum, L
c) one from its total angular momentum, J (sum of those two components).
Corresponding to these three moments there are three different g-factors.

Electron spin g-factor

The most known of these is the electron spin g-factor (more often called simply the electron g-
factor), ge, defined by:

𝜇𝐵
𝜇𝑠 = 𝑔𝑒 𝑆
ℏ

where 𝜇𝑠 is the magnetic moment resulting from the spin of an electron, S is its spin angular
𝑒ℏ
momentum, and 𝜇𝐵 = is the Bohr magneton. In atomic physics, the electron spin g-factor
2𝑚𝑒
is often defined as the absolute value or negative of 𝑔𝑒 :

𝑔𝑠 = |𝑔𝑒 | = −𝑔𝑒

The z-component of the magnetic moment then becomes:

𝜇𝑧 = −𝑔𝑠 𝜇𝐵 𝑚𝑠

Electron orbital g-factor

The electron orbital g-factor, 𝑔𝐿 , is defined by:

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𝜇𝐵
𝜇𝐿 = 𝑔𝐿 𝐿
ℏ

where 𝜇𝐿 is the magnetic moment resulting from the orbital angular momentum of an electron, L is
its orbital angular momentum, and 𝜇𝐵 is the Bohr magneton.

For an infinite-mass nucleus, the value of 𝑔𝐿 is exactly equal to one. For a finite-mass nucleus,
there is an effective g value;

1
𝑔𝐿 = 1 −
𝑀

where M is the ratio of the nuclear mass to the electron mass.

Total angular momentum (Landé) g-factor

The Landé g-factor, 𝑔𝐽 is defined by:

𝜇𝐵
𝜇 = 𝑔𝐽 𝐽
ℏ

where μ is the total magnetic moment resulting from both spin and orbital angular momentum of
an electron, J = L + S is its total angular momentum, and 𝜇𝐵 is the Bohr magneton.

𝑗(𝑗 + 1) + 𝑠(𝑠 + 1) − 𝑙(𝑙 + 1)

𝑔𝐿 = 1 +
2𝑗(𝑗 + 1)

Landé Splitting Factor (g factor)

This a factor in the formula for the splitting of energy levels in a magnetic field that determines
the scale of splitting in relative units.

It also determines the relative magnitude of the gyromagnetic ratio.

The Landé splitting factor was introduced by the German physicist A. Landé in 1921.

Its value is different for different energy levels of the atom and depends on how the orbital and
spin angular momenta of the individual electrons are coupled.

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If the total orbital and total spin moments of the atom and their sum (the moment of the atom as
a whole) are given by the quantum numbers L, S, and J, the atomic Landé splitting factor is
determined by Landé’s formula:

𝑗(𝑗 + 1) + 𝑠(𝑠 + 1) − 𝑙(𝑙 + 1)

𝑔 =1+
2𝑗(𝑗 + 1)

For a purely orbital moment (𝑆 = 0, 𝐽 = 𝐿), the Lande splitting factor is equal to 1, and for a
purely spin moment (𝐿 = 0, 𝐽 = 𝑆), it is equal to 2.

Exercise

Calculate the value of Londe g-factor for a single valence electron atom corresponding to its P
state with no spin moment.

Solution

𝑗(𝑗 + 1) + 𝑠(𝑠 + 1) − 𝑙(𝑙 + 1)

𝑔 =1+
2𝑗(𝑗 + 1)

𝑙 = 1 𝑎𝑛𝑑 𝑠 = 0

𝑔=1

Example

Calculate the Lande g factor for the term 5𝐹2 ?

Solution

(2𝑠+1)
From the notation 𝐹𝑗 implying that 𝑗 = 2.

2𝑠 + 1 = 5 ⟹ 𝑠 = 2

State f implies that 𝑙 = 3.

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𝑗(𝑗 + 1) + 𝑠(𝑠 + 1) − 𝑙(𝑙 + 1) 2(2 + 1) + 2(2 + 1) − 3(3 + 1)

𝑔 =1+ = 1+
2𝑗(𝑗 + 1) 2𝑥3(3 + 1)

𝑔=1

Example

Calculate the Lande g factor for the term 4𝑑1⁄2 ?

Solution

(2𝑠+1)
From the notation 𝑑𝑗 implying that 𝑗 = 1⁄2.

2𝑠 + 1 = 4 ⟹ 𝑠 = 3⁄2

State d implies that 𝑙 = 2.

𝑗(𝑗 + 1) + 𝑠(𝑠 + 1) − 𝑙(𝑙 + 1)

𝑔 =1+
2𝑗(𝑗 + 1)

1⁄ (1⁄ + 1) + 3⁄ (3⁄ + 1) − 2(2 + 1)

𝑔 = 1+ 2 2 2 2
2𝑥3(3 + 1)

𝑔=0

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11.0 Electronic Configuration

Electron configuration is the distribution of electrons of an atom in atomic orbitals. Each electron
is described as moving independently in an orbit with a given energy level. The knowledge of the
electron configuration of different atoms is useful in understanding the structure of the periodic
table of elements. This is also useful for describing the chemical bonds that hold atoms together.

Shells and Subshells

Bohr and Somerfield introduced the concept of shells and subshells. An electron shell is the orbital
label given by principal quantum number, 𝑛. An atom's nth electron shell can accommodate 2𝑛2
electrons, e.g. the first shell can accommodate 2 electrons, the second shell 8 electrons, the third
shell 18 electrons and so on. The factor of two arises because the allowed states are doubled due
to electron spin—each atomic orbital admits up to two otherwise identical electrons with opposite
spin, one with a spin +1/2 (usually denoted by an up-arrow) and one with a spin −1/2 (with a down-
arrow).

A subshell is the set of states defined by a common azimuthal quantum number, ℓ, within a shell.
The value of ℓ is in the range from 0 to 𝑛 − 1. The values ℓ = 0, 1, 2, 3 correspond to the s, p, d,
and f labels, respectively. For example, the 3d subshell has 𝑛 = 3 and ℓ = 2. The maximum
number of electrons that can be placed in a subshell is given by 2(2ℓ + 1). This gives two electrons
in an 𝒔 subshell, six electrons in a 𝒑 subshell, ten electrons in a 𝒅 subshell and fourteen electrons
in an 𝒇 subshell.

The Pauli Exclusion Principle

In 1925, the Austrian physicist Wolfgang Pauli proposed the following rule: No two electrons can
have the same set of quantum numbers.

The quantum numbers involved to specify the state of an electron is a set of four numbers
1
(𝑛, 𝑙, 𝑚𝑙 , 𝑚𝑠 ). For example, the quantum numbers (2, 1, 0, − ) completely specify the state of an
2

electron in an atom. Note that 𝑛 determines the energy state in the absence of a magnetic field.

There are no two electrons that can be in the same state. This statement is known as the Pauli
exclusion principle, because it excludes electrons from being in the same state.
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Example

List the possible set of quantum numbers when 𝑛 = 1 and 𝑙 = 0.

Solution

When energy level 𝑛 = 1, the only value 𝑙 can have is 0 and thus 𝑚𝑙 can only be 0. The spin
projection 𝑚𝑠 can be either +1/2 or −1/2, and so there can be two electrons in the 𝑛 = 1 state.
1 1
One has quantum numbers (1, 0, 0, + 2) and the other (1, 0, 0, − 2).

This illustrates that there can only be one or two electrons having 𝑛 = 1. If there are two electrons
in the 𝑛 = 1 level, their spins must be in opposite directions. A third electron must reside in the
higher-energy 𝑛 = 2 level.

Spectroscopic Notation
Standard notations are used to indicate the electron configurations of atoms in physics and
chemistry. The notation consists of a sequence of atomic subshell labels with the number of
electrons assigned to each subshell placed as a superscript.

The table below shows the letters used to label azimuthal quantum number 𝑙.

The electronic configuration notation is of the form;

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Example

Hydrogen has one electron in the s-orbital (subshell) of the first (𝑛 = 1)shell, so its configuration
is written 1𝑠1 .

Lithium has two electrons in the 1s-subshell and one in the (𝑛 = 2) 2s-subshell, so its configuration
is written 1𝑠 2 2𝑠1 .

Ground State and Excited States

The energy associated to an electron is that of its orbital. The energy of a configuration is often
approximated as the sum of the energy of each electron, neglecting the electron-electron
interactions. The configuration that corresponds to the lowest electronic energy is called the
ground state. Any other configuration is an excited state.

Example

The ground state configuration of the sodium atom is 1𝑠 2 2𝑠 2 2𝑝6 3𝑠1 . The first excited state is
obtained by promoting a 3𝑠 electron to the 3𝑝 orbital, to obtain the 1𝑠 2 2𝑠 2 2𝑝6 3𝑝1 configuration,
abbreviated as the 3𝑝 level. Atoms can move from one configuration to another by absorbing or
emitting energy. In a sodium-vapor lamp, sodium atoms are excited to the 3𝑝 level by an electrical
discharge, and return to the ground state by emitting yellow light of wavelength 589 𝑛𝑚.

Exercise

List all the possible sets of quantum numbers for the shell 𝑛 = 2.

Determine the number of electrons that can be in each subshell.

How many electrons can be in the Shell 𝑛 = 2?

Solution

Given 𝑛 = 2 for the shell, the rules for quantum numbers limit 𝑙 to be 0 or 1. The shell 𝑛 = 2 has
two subshells, labelled 2s and 2p. Since the lowest l subshell fills first, we start with the 2s subshell
possibilities and then proceed with the 2p subshell.

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Exercise

How many subshells are in the shell 𝑛 = 3?

Identify each subshell using labels.

Calculate the maximum number of electrons that will fit into each subshell.

Write the subshells in the configuration notation.

Solution

𝑛 = 3 ⟹ 𝑙 = 0, 1, 2 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠 (𝑛 − 1) The subshells are three.

3𝑠, 3𝑝 and 3𝑑

3𝑠 ℎ𝑎𝑠 𝑙 = 0 𝑡ℎ𝑢𝑠 2(2𝑙 + 1) = 2(0 + 1) = 2

3𝑝 ℎ𝑎𝑠 𝑙 = 1 𝑡ℎ𝑢𝑠 2(2𝑙 + 1) = 2(2 𝑥 1 + 1) = 6

3𝑑 ℎ𝑎𝑠 𝑙 = 2 𝑡ℎ𝑢𝑠 2(2𝑙 + 1) = 2(2 𝑥 2 + 1) = 10

3𝑠 2 3𝑠 6 3𝑠10

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Exercise

Prove that the maximum number of electrons in a shell is 2𝑛2 .

Solution

For each value of 𝑙 we have 2(2𝑙 + 1) electrons.

For a given value of 𝑛, we have 𝑙 = 0, 1, 2, … , (𝑛 − 1)
𝑛−1

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑎 𝑠ℎ𝑒𝑙𝑙, 𝑁 = ∑ 2(2𝑙 + 1)

0

𝑁 = 2(2(0) + 1) + 2(2(1) + 1) + 2(2(2) + 1) + ⋯ + 2(2(𝑛 − 1) + 1)

𝑁 = 2{(2(0) + 1) + (2(1) + 1) + (2(2) + 1) + ⋯ + (2(𝑛 − 1) + 1)}
𝑁 = 2{1 + 3 + 5 + ⋯ + (2𝑛 − 1)}
𝐵𝑢𝑡 𝑡ℎ𝑒 𝑠𝑒𝑟𝑖𝑒𝑠 1 + 3 + 5 + ⋯ + (2𝑛 − 1) = 𝑛2 ⟹ 𝑁 = 2𝑛2

Exercise

1) a) If one subshell of an atom has 9 electrons in it, what is the minimum value of 𝑙?
b) What is the spectroscopic notation for this atom, if this subshell is part of the 𝑛 = 3 shell?
a) 2(2𝑙 + 1) > 9 ⟹ 2𝑙 > 3.5 𝑜𝑟 𝑙 > 1.7
𝑀𝑖𝑛𝑖𝑚𝑢𝑚 𝑙 = 2
b) 3𝑑 9
2) a) What is the minimum value of 𝒍 for a subshell that has 11 electrons in it?
b) If this subshell is in the 𝑛 = 5 shell, what is the spectroscopic notation for this atom?
3) a) How many electrons can be in the 𝑛 = 4 shell?
b) How many subshells, and how many electrons can be in each?
(a) 32
(b) 2 in s, 6 in p, 10 in d and 14 in f, for a total of 32.
4) a) List all possible sets of quantum numbers (𝑛, 𝑙, 𝑚𝑙 , 𝑚𝑠 ) for the 𝑛 = 3 shell.
b) Determine the number of electrons that can be in the shell and each of its subshells.

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