Chapter 1

Bohr Atomic Model

Electromagnetic spectrum

This is a series of radiation energies arranged in order of their wavelengths or

frequencies. The energy of a radiation is given by
ℎ𝐶
𝐸 = ℎ𝑣 = ……………………………………… 1.1
𝜆

Where h is the Plank’s constant, C speed of electromagnetic radiation and 𝜆 is the

wavelength.
𝐶
𝜆 = 𝑣 ……………………………………………… 1.2

1 𝑣
= 𝐶 ……………………………………………… 1.3
𝜆

1
is called the wave number measured in 𝑐𝑚−1 , 𝑚−1 , 𝑛𝑚−1 (10−9 𝑚)
𝜆

𝐶
𝑣 = 𝜆 ……………………………………… 1.4

The energy of a radiation can be given in form of Joules, electron-Volt , wavenumber or

frequency. The Plank’s Constant ℎ = 6.64 × 10−34 𝐽𝑆 and 1𝑒𝑉 = 1.602 × 10−19 𝐽, 𝐶 =
3.0 × 108 𝑚𝑠 −1

Examples

1. A radiation has Energy E of 10J. Find;

a) Energy in eV
b) Frequency of the radiation
c) Wavelength of the radiation
d) Wave number

Solution

Electron volt (eV) is the energy possessed by an electron accelerated by a voltage of

1volt. But the charge of an electron is 1.602 × 10−19 𝐶

1𝑒𝑉 = 1.602 × 10−19 𝑉𝐶 = 1.602 × 10−19 𝐽

 1
10𝐽 = 1.602×10−19 𝐽 × 10 = 6.24 × 1019 𝑒𝑉

Frequency
𝐸 10
𝑣 = ℎ = 6.64×10−34 𝐽𝑆 = 1.5092 × 1034 𝐻𝑧

Wavelength
𝐶 3.0×108 𝑚/𝑠
𝜆 = 𝑣 = 1.5092×1034 /𝑠 = 1.992 × 10−25 𝑚

Wave number
1 𝑣 1
= 𝐶 = 1.992×10−25 𝑚 = 5.02 × 1024 𝑚−1
𝜆

BOHR ATOMIC MODEL

Neils Bohr tried to explain the experimental observations of Rutherfold that an atom

 Has a positive centre that is massive and very small as compared to electron cloud
 That an atom that is illuminated with radiation absorbs radiation and emits
radiation

Assumptions (Postulates) of the Bohr Atomic Theory

i. An electron in an atom moves in circular orbits under the action of coulomb force
of the nucleus
ii. The orbits are not continuous but the allowed orbits in which the electrons revolve
are the ones in which the angular momentum L is an integer multiple of the Plank’s
Constant divided by 2π
iii. Electrons in allowed orbits do not radiate energy
iv. Electromagnetic radiation is emitted when an electron moves from one energy
level to another and the energy of the radiation is equal to the energy difference
between the two orbits

Let E be given by ∆𝐸 = ℎ𝑣 and 𝐸𝑖 𝑎𝑛𝑑 𝐸𝑓 be the initial and the Energies of the initial and
the final orbits occupied by the electron;

The frequency of the photon emitted is given by

 (𝐸𝑖 − 𝐸𝑓 )
𝑣= ………………………………………………… 2.1
ℎ

Considering the Hydrogen atom, the nucleus has a mass 𝑀 and a charge +𝑍𝑒 and a
single electron of charge – 𝑒 and mass 𝑚𝑒 . If the radius of the orbit is 𝑟 and assuming that
the nucleus is at rest, the acceleration of the electron is;
𝑣2
𝑎𝑐 = ………………………………………………………………… 2.2
𝑟

𝑣 is the electron tangential speed. The centripetal force is provided by the attraction of
the electron and the nucleus thus;
𝑍𝑒 2
𝐹 = 4𝜋𝜀 2 ……………………………………………………………… 2.3
0𝑟

The attractive force should be equal to the centripetal force due to angular motion of the
electron
𝑍𝑒 2 𝑣2
= 𝑚𝑒 …………………………………………………… 2.4
4𝜋𝜀0 𝑟2 𝑟𝑒

From 2.4
𝑍𝑒 2
𝑣 2 = 4𝜋𝜀 ………………………………………………… 2.5
0 𝑚𝑒 𝑟

According to second assumption

𝑛ℎ
𝐿 = 2𝜋 …………………………………………………………… 2.6

Where n is a positive integer called the quantum number and L is the angular
momentum

𝐿 = 𝑟 × 𝑝 ……………………………………………………… 2.7

From uniform circular motion the vector 𝑟 is perpendicular to its momentum thus;

𝐿 = 𝑟𝑝 = 𝑚𝑒 𝑟𝑣 …………………………………………… 2.8

Replacing L in 2.6
 𝑛ℎ
𝑚𝑒 𝑟𝑣 = 2𝜋 ………………………………………………………… 2.9

Making 𝑣 the subject

𝑛ℎ
𝑣 = 2𝜋𝑚 ……………………………………………………… 2.10
𝑒𝑟

Replacing 𝑣 in equation 2.5 and making r the subject we get

(4𝜋𝜀0 )2 ℎ 2𝑛 2 𝑎0 𝑛 2
𝑟= = ……………………………………… 2.11
4𝜋𝑚𝑒 𝑧𝑒 2 𝑍

For H- atom 𝑍 = 1 𝑎𝑛𝑑 𝑛 = 1 for orbit quantum number 1.

(4𝜋𝜀0 )2ℎ 2 𝑛 2
𝑎0 = …………………………………………… 2.12
4𝜋𝑚𝑒 𝑧𝑒 2

𝑎0 is a constant called the first Bohr radius of the Hydrogen atom and it is the radius of
the orbit of the hydrogen atom in the ground state. Substituting the values of the
constants in equation 2.12

𝑎0 = 5.29 × 10−11 𝑚 ……………………………………… 2.13

Similarly comparing 10 and 11 and replacing r in 2.10

2𝜋𝑒 2 𝑍
𝑣 = (4𝜋𝜀 ……………………………………………….. 2.14
0 )𝑛ℎ

For hydrogen 𝑛 = 1 𝑎𝑛𝑑 𝑍 = 1 and comparing with speed of light

𝑣 2𝜋𝑒 2 1
= (4𝜋𝜀 = 𝛼 = 137………………………………….. 2.15
𝑐 0 )ℎ𝑐

𝛼 is the Sommerfeld fine structure constant

The frequency of revolution of the electron round the orbit is;

𝑣
𝑓 = 2𝜋𝑟 …………………………………………………… 2.16

Substituting the values of 𝑟 and 𝑣

4𝜋𝑚𝑒 𝑒 4 𝑍 2
𝑓 = (4𝜋𝜀 2 𝑛 3ℎ 3 ……………………………………………. 2.17
0)
Kinetic Energy

The total kinetic energy of the system is given by

𝑚𝑣 2
𝐾. 𝐸 = …………………………………………………. 2.18
2

The total energy of the electron is the sum of K.E and P.E
𝑚𝑣 2 𝑍𝑒 2
𝐸 = 𝐾. 𝐸 + 𝑃. 𝐸 = −
2 4𝜋𝜀0𝑟

𝑍𝑒 2 𝑍𝑒 2 𝑍𝑒 2
𝐸 = 2(4𝜋𝜀 )𝑟
− 4𝜋𝜀 = − 2(4𝜋𝜀 ………………………………….2.19
0 0𝑟 0 )𝑟

From equation 2.19, E approaches zero as r approaches infinity thus the total energy of
the atom is zero when the atom is ionized.

Replacing 𝑟 in 2.19

2𝜋𝑚𝑒 𝑒 4 𝑍 2
𝐸 = (4𝜋𝜀 2 ℎ3 𝑛2 …………………………………………………..2.20
0)

But the energy of a photon is the energy difference between the transition states

2𝜋𝑚𝑒 𝑒 4 𝑍 2 1 1
∆𝐸 = 𝐸𝑖 − 𝐸𝑓 = ℎ𝑣 = (4𝜋𝜀0 )2 ℎ 2
(𝑛 2 − 𝑛 2 )
𝑖 𝑓

2𝜋𝑚𝑒 𝑒 4 𝑍 2 1 1
𝑣= (4𝜋𝜀0)2 ℎ 3
(𝑛 2 − 𝑛 2 )
𝑖 𝑓

1 𝑣
The wave number 𝜆 = 𝐶

1 𝑣 2𝜋𝑚 𝑒 4 𝑍 2 1 1
= 𝐶 = 𝑣̅ = (4𝜋𝜀 𝑒)2 𝑐ℎ3 (𝑛 2 − 𝑛 2 )
𝜆 0 𝑖 𝑓
 2𝜋𝑚𝑒 𝑒 4
Letting 𝑅∞ = (4𝜋𝜀 2𝑐ℎ 3
0)

1 𝑣 1 1
= 𝐶 = 𝑣̅ = 𝑅∞ 𝑍 2 (𝑛 2 − 𝑛 2 ) …………………………………… 2.22
𝜆 𝑖 𝑓

Assuming that the nucleus is at rest and substituting the values of the constants;’
13.6(𝑒𝑉)𝑍 2
𝐸= ………………………………………………… 2.23
𝑛2

𝑅∞ = 109737𝑐𝑚−1

𝑛 can take the values 1,2,3,4…………∞

Where 𝑛 = 1 the lowest energy state and it is called ground and all higher states are
referred to as excited states

Naturally the electron stays in ground state unless it absorbs enough energy to jump to
any of the higher levels. This can occur if an electron absorbs a photon of energy equal
to the energy difference between the two levels of transition.

When an electron is excited it falls back to lower levels and finally to ground state emitting
a photon of a specific energy equal to the energy difference between the two states.

Transitions from higher states to level 𝑛 = 1,2,3,4,5 give a series of closely spaced
spectral lines for each value of n that lie at different regions of the electromagnetic
spectrum.

The energies of the different energy levels are as follows:

 Energy Level Principal Quantum Number Energy (eV)
(n)
K 1 -13.6
L 2 -3.4
M 3 -1.51
N 4 -0.85
O 5 -0.54

The transitions to the lower 5 energy levels give the spectral series of hydrogen
represented in an energy level diagram below;

EXAMPLES

An atom of hydrogen emits a photon with Energy (E) of 1.55 eV. Determine the wave
number for this photon, the frequency and the wavelength

Solution

Converting energy into Joules

1𝑒𝑉 = 1.602 × 10−19 𝐽

1.55𝑒𝑉 = 1.602 × 10−19 𝐽/𝑒𝑉 × 1.55𝑒𝑉

= 2.483 × 10−19 𝐽
ℎ𝑐
𝐸= 𝜆

1 𝐸 2.483×10−19𝐽
= ℎ𝑐 = 6.64×10−34𝐽𝑆×3.0×108 𝑚/𝑆 = 1.246 × 106 𝑚−1
𝜆

In the Bohr’s atomic theory it is assumed that the nucleus is stationary remaining at rest
at the centre of the orbit. This can only be true if the nucleus had an infinite mass.

However, the nucleus and the electron in the atom move about their common centre of
mass (CM) so that if we let r be the distance between the electron and the nucleus, r’ be
distance of the nucleus from the CM and re be the distance of the electro from the CM,
Then;

𝑀𝑟 ′ = 𝑚𝑒 𝑟𝑒 …………………………………………………………………….. 2.25

𝑟 = 𝑟 ′ + 𝑟𝑒 ………………………………………………………………………. 2.26
𝑀𝑟
𝑟𝑒 = 𝑀+𝑚 ……………………………………………………………………….. 2.27
𝑒

𝑚 𝑟
𝑟 ′ = 𝑀+𝑚
𝑒
……………………………………………………………………… 2.28
𝑒

Total angular momentum of the system (L) is given by;

𝐿 = 𝐼𝜔 = 𝜔 (𝑀𝑟′2 + 𝑚𝑒 𝑟𝑒 2 ) ………………………………………….. 2.29

Substituting r’ and re from equation 2.27 and 2.28 in 2.29 we get;

𝑚𝑒 𝑀𝜔𝑟 2
𝐿= = 𝜇𝜔𝑟 2 …………………………………………………………. 2.30
𝑚𝑒 +𝑀

𝑚 𝑀
Where reduced mass 𝜇 = 𝑚 𝑒+𝑀
𝑒

But 𝜔𝑟 = 𝑣 thus equation 2.30 becomes

𝑛ℎ
𝐿 = 𝜇𝑣𝑟 = 2𝜋 …………………………………………………………………. 2.31

The centripetal force acting on the electron is;

𝑚𝑒 𝑀𝑟𝜔2
𝑚𝑒 𝑟𝑒 𝜔2 = = 𝜇𝜔2 𝑟 ………………………………………………………. 2.32
𝑚𝑒 +𝑀
Equating equation 3.32 with coloumb force on the electron;
𝑍𝑒 2 𝜇𝑣 2
𝜇𝜔2 𝑟 = (4𝜋𝜀 )𝑟 2
=
0 𝑟

𝑍𝑒 2 𝑚𝑒 𝑣 2
This is the same equation as 𝐹 = (4𝜋𝜀 )𝑟 2
= but 𝜇 replaces 𝑚𝑒 thus equation
0 𝑟

2𝜋𝑚 𝑍 2𝑒 4 2𝜋𝜇𝑍 2 𝑒 4
𝑅∞ = (4𝜋𝜀 𝑒)2𝑐ℎ3 changes to R given by𝑅 = (4𝜋𝜀 2 𝑐ℎ 3
0 0)

𝑅∞
𝑅= 𝑚 ……………………………………………………………… 2.33
1+ 𝑒
𝑀

1
NB: The Rydberg constant R is less than 𝑅∞ by 1+(𝑚 . R is therefore not the same for
𝑒 ⁄𝑀 )
all atoms. The Bohr atomic model succeeded in explaining:

i. The distinct spectral lines of hydrogen

ii. Predicting the energies of electrons in different energy levels

However, it could not explain, the fine structure and could not explain the arrangement of
electrons in energy levels as well as explain the spectra of multi electron systems:

Sommerfeld Model of the Atom

In order to explain the fine structure, Sommerfeld made the following assumptions:

1. That the atomic orbits are not spherical but elliptical with the nucleus located near
one end of the ellipse.
2. That the circular orbit predicted by Bohr was just a limiting case of the Elliptical
orbit when the Semi major axis was equal the semi minor axis.

The model thus introduced another quantum number the Azimuthal quantum number.
However, it could not

i. Predict the exact number of fine structure components

ii. It could not explain the arrangement of electrons in multi electron systems
iii. Could not explain the Zeeman and the Stack Effect
iv. Could not explain the Hyperfine structure
 Wave Mechanics model of the Atom

Various practical observations could not be explained by the two quantum numbers
suggested by the Sommerfeld Model of the atom.

For example, many spectral lines actually consist of two separate lines that are very close.
For instance the first line of the Balmer series (Hα) is expected to be a single line of
wavelength 656.3 nm. However, two lines 0.14 nm apart are actually observed.

To account for these, wave mechanics in the process of solving the Schrodinger wave
equation for Hydrogen, the integers n, l, and m are introduced. They are referred to as
quantum numbers. The quantum numbers describe the states of system. The values of
the quantum numbers are:

𝑛 = 1,2,3,4 … … … … … ∞

𝑙 = 0,1,2,3 … … . 𝑛 − 1

𝑚 = 𝑙, 𝑙 − 1, 𝑙 − 2, … … .0, … … . −𝑙……………………………………….. 3.1

The quantum numbers l and m are related to the magnitude L of the orbital angular
momentum such that m is the z-component (Lz) of L.

The magnitude of the orbital angular momentum L and that of Lz are given by
ℎ
𝐿 = 2𝜋 (𝑙(𝑙 + 1))

ℎ
𝐿𝑧 = 𝑚 2𝜋 ……………………………………………………………………. 3.2

The quantum number n gives the quantization of the energy and therefore specifies the
energy level in which the electron occupies consequently giving the energy of the electron

𝑙 gives the magnitude of the Angular momentum and therefore splits the energy level into
orbitals of slightly different energies

𝑚 specifies the orientation of the angular momentum of the electron in an external

magnetic field.

Atomic Orbitals

The solution of the Schrodinger equation represents the wave function 𝜓𝑛𝑙𝑚 (𝑟, 𝜃, 𝜑)
referred to as one electron system called atomic orbital. These atomic orbital are
described by the quantum numbers n,l and m. They differ from Bohr’s Orbit in the
following ways

1. Orbits refer to definite path followed by the electron around the nucleus
characterized by quantum number n. Orbitals are proposed spaces around the
nucleus where there is a finite probability of finding the electron at a given instance
and that the square of the wave function gives the probability of finding the electron
at a given point in space characterized by the quantum numbers n,l and m.
2. The representation of the orbit is two dimensional while that of the orbital is 3
dimensional involving the spherical polar coordinates 𝑟, 𝜃, 𝜑
3. An orbit having principal quantum number n can accommodate 2n 2 electrons.

Orbitals have different values of 𝑙 and each orbital has a letter symbol as follows:
 Value of 𝑙 0 1 2 3 4 5 6
Letter Symbol s p d f g h i

The representation of the orbitals indicates the value of n and the symbol of the orbital
e.g. 1s, 2s, 3d etc.

Electron Spin

Wave mechanics by the Schrodinger was inadequate to explain all the practical
observations in the spectrum of Hydrogen and other simple atoms. In other words the
quantum numbers n,l and m seem inadequate to explain the following:

i. Many spectral lines consist of two separate lines that are very close
ii. The number of transitions (lines) observed when atoms were placed in a magnetic
field could not be accounted. i.e. Zeeman Effect could not be explained
iii. The number of transitions observed when the atoms were placed in an electric field
could not be explained (Stack effect could not be explained)
iv. Could not explain the arrangement of electrons in energy levels for multi electron
species

These inadequacies of the wave mechanics were solved by the Vector model of the atom

Vector Representation of Momenta and Vector Coupling Approximations

From above, it appears that another quantum number is needed for which the number of
projections on the Z-axis is even. To account for this Uhlenbeck and Goudsmit in 1925
assigned a new angular momentum to the electron.

The vector model of the atom suggests that the electron possesses Orbital Angular
Momentum associated with the orientation of the orbital in external magnetic field as well
as the Spin Angular Momentum resulting from the Spin of the electron about its axis.

ℎ ̅
ℎ
The electron thus was assigned a spin angular momentum equal to 𝑠 = 1⁄2 (2𝜋 ) = 2 . The
spin Angular momentum is quantized with quantum number ms such that;
ℎ 1⁄
𝑠 = (2𝜋 ) [𝑠(𝑠 + 1)] 2 …………………………………………………… 3.1

The Spin magnetic quantum number specifies the orientation of the spin angular
momentum in an external magnetic field along the z axis so that:
 ℎ
𝑠𝑧 = 𝑚𝑠 (2𝜋 ) ………………………………………………………………… 3.2

Where 𝑚𝑠 = ± 1⁄2 is the called the spin magnetic quantum number.

Spin –orbit interaction

Consider an electron of charge 𝑒 moving in a Bohr’s orbit around a nucleus of charge

+𝑍𝑒. Let the velocity of the electron relative to the nucleus be 𝑣 and its position relative
to the nucleus be 𝑟. Since the motion is relative, we consider the electron to be at rest
while the nucleus is moving round the electron with a velocity – 𝑣 in a circle of radius 𝑟.

+Ze

The motion of the nucleus constitutes a current loop which produces a magnetic field and
the electron is located at the centre of the loop. Let a current element 𝑗 be induced due to
motion of the nucleus. Then

𝑗 = −𝑍𝑒𝑣 ………………………………………………………………………… 3.3

From Ampere’s law
𝜇0 𝑗×𝑟 𝑍𝑒𝜇0 𝑣×𝑟
𝐵= = ………………………………………………………… 3.4
4𝜋𝑟 3 4𝜋𝑟 3

from Coloumb’s law of force, the force between the electron and the nucleus is given by
𝑍𝑒
𝐹 = 4𝜋𝜀 2 and the electric field E is given by
0𝑟

𝑍𝑒𝑟̅
𝐸= …………………………………………………………………… 3.5
4𝜋𝜀0 𝑟 3

From equations 3.4 and 3.5 making B the subject and replacing 1/𝜀0 𝜇0 with 𝑐 2
𝑣×𝐸
𝐵 = 𝜀0 𝜇0 𝑣 × 𝐸 = ………………………………………………………………… 3.6
𝑐2

The quantity 𝐵 is the magnetc field strength experienced by the electron when it is orbiting
with velocity 𝑣 relative to the nucleus and therefore through the electric field strength E
which the nucleus exerts on it. The spin-orbit interaction energy ∇𝐸 results from the
interaction between the field 𝐵 and the spin magnetic moment.
𝑔𝑠 𝑒𝑠 2𝜋𝑔𝑠 𝛽𝑒 𝑠
𝜇𝑠 = − =− ……………………………………………………………. 3.7
2𝑚𝑒 ℎ

The orientational potential energy of the spin magnetic moment in this magnetic field is

∇𝐸 = −𝜇𝑠 . 𝐵 …………………………………………………………………… 3.8

Using equation 3.7

2𝜋𝑠.𝐵
∇𝐸 = 𝑔𝑠 𝛽𝑒 …………………………………………………………………… 3.9
ℎ

But the energy has been evaluated in frame of reference in which the electron is at rest
but the nucleus should be considered to be at rest. This transformation reduces the
orientational potential energy by a factor of 2, thus:
𝜋𝑠.𝐵
∇𝐸 = 𝑔𝑠 𝛽𝑒 ………………………………………………………………………….. 3.10
ℎ

Putting 𝐹 = −𝑒𝐸 in 3.6 we have

𝑣×𝐹
𝐵= ………………………………………………………………………… 3.11
𝑒𝑐 2

𝑑𝑉 𝒓̅
Also 𝐹 = − 𝑑𝑟 𝑟 in 3.11

𝑣×𝑟 𝑑𝑉
𝐵 = 𝑒𝑐 2𝑟 𝑑𝑟 ………………………………………………………………………………… 3.12
 𝑟×𝑝 𝑑𝑉
𝐵=𝑚
𝑒 𝑒𝑐 2 𝑟 𝑑𝑟

But 𝐿 = 𝑟 × 𝑝

Thus
𝐿 𝑑𝑉
𝐵=𝑚 2 ……………………………………………………………………………. 3.13
𝑒 𝑒𝑐 𝑟 𝑑𝑟

Thus the magnetic field experienced by the electron due to its motion round the nucleus
is directly proportional to Angular momentum 𝑙 and it’s in the direction of 𝑙
2𝜋𝛽𝑒 𝑑𝑉
∆𝐸 = 𝑚 3 𝑙. 𝑠 …………………………………………………………………….. 3.14
𝑒 𝑒ℎ𝑐 𝑟 𝑑𝑟

Pauli Exclusion Principle

In a Multi electron atom there can never be any more than one electron with the same
quantum state. i.e. the 4 quantum numbers the same. Using this principle electrons can
be assigned quantum states as follows:

i. Electrons with same 𝑛 value belong to the same shell or energy level
ii. For a given value of 𝑛 electrons with the same value of 𝑙 belong to the same
subshell (orbital)

Electrons in a Shell

Electrons with the same value of 𝑛 but different values of 𝑙 thus they are in different
orbitals. For a given value of 𝑛, 𝑙 can have 0, 1,2 … . 𝑛 − 1.

Electrons in a Sub shell (Orbital)

Have the same values of 𝑛 and 𝑙 but differ by the quantum numbers 𝑚𝑙 and 𝑚𝑠 .

𝑚𝑙 can have the values 𝑙, 𝑙 − 1, 𝑙 − 2 … … 0 … … . . −𝑙. This corresponds to 2𝑙 + 1 integral

values.

The quantum number 𝑚𝑠 can have the values ± 1⁄2 thus the total number of quantum
states that can exist for electrons with the same values of 𝑛 and 𝑙 are 2(2𝑙 + 1). This
implies that there can be 2(2𝑙 + 1) electrons in a subshell of quantum number 𝑙. The
maximum number of electrons that can be accommodated in a shell of principal quantum
number 𝑛 is 2𝑛2 .

Example

Find the maximum number of electrons that can be accommodated:

 i. 3d orbital

To have d orbital, 𝑙 = 2

𝑁𝑜 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑎 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 = 2(2𝑙 + 1) = 2(2 × 2 + 1) = 10

ii. 4s orbital

𝑙 = 0,

2(2𝑙 + 1) = 2(2 × 0 + 1) = 2

iii. 2p orbital
𝑙 = 1,

2(2𝑙 + 1) = 2(2 × 1 + 1) = 6

iv. 𝑛 = 3 shell

𝑥 = 2𝑛2

𝑥 = 2 × 32 = 18

Configuration

3s23p63d10

Electron Configuration

Refers to the arrangement of electrons in atoms. This is done by indicating the principal
quantum number n, representing the orbital by its letter Symbol and the number of
electrons as a superscript. Electrons are filled starting with the lowest energy level 𝑛 = 1.

l- Value 0 1 2 3 4 5 6
Symbol s p d f g h i
Maximum no. 2 6 10 14 18 22 26
of Electrons

The energy levels also have letter symbols

 Shell n-Value Maximum no. of electrons
K 1 2
L 2 8
M 3 18
N 4 32

Three general rules are applied in filling electrons in orbitals

Pauli Exclusion Principle

No more than one electron can have the same quantum state at the same time. Orbitals
with the same n and l values have the same energy. Orbitals with the same energy are
said to degenerate. E.g. Orbitals in the 2p sublevel are degenerate orbitals – Which
means that the 2px, 2py, and 2pz orbitals have the exactly same energy, as illustrated in
the diagram provided below. Similarly, the 3p x, 3py, and 3pz are degenerate orbitals. And
at the 3d energy level, the 3dxy, 3dxz, 3dyz, 3dx2 – y2, and 3dz2 are degenerate orbitals with
the same energy.

The number of different orbitals with the same energy is called the degeneracy of the
orbitals, e.g.

 The degeneracy of p orbitals is 3

 The degeneracy of d orbitals is 5
 The degeneracy of f orbitals is 7
The Aufbau Principle
It states that in the ground state of an ion or an atom, the atomic orbitals of the
electrons fill the lowest available energy levels before they occupy the higher levels. For
instance, 2s subshell is filled after the 1s shell is occupied. Hence the most stable electron
configuration is achieved.
Aufbau principle tells us that the lowest energy orbitals get filled by electrons first. After
the lower energy orbitals are filled, the electrons move on to higher energy orbitals. The
problem with this rule is that it does not tell about the three 2p orbitals and the order that
they will be filled in.

Hunds Rule of Maximum Multiplicity

Hunds Rule of Maximum Multiplicity rule states that for a given electron configuration, the
term with maximum multiplicity falls lowest in energy. According to this rule electron
pairing in p, d and f orbitals cannot occur until each orbital of a given subshell contains
one electron each or is singly occupied.

According to Hund’s rule:

 Before the double occupation of any orbital, every orbital in the sub level is singly
occupied.
 For the maximization of total spin, all electrons in a single occupancy orbital have
the same spin.
An electron will not pair with another electron in a half-filled orbital as it has the ability to
fill all its orbitals with similar energy. Many unpaired electrons are present in atoms which
are at the ground state. If two electrons come in contact they would show the same
behaviour as two magnets do. The electrons first try to get as far away from each other
as possible before they have to pair up.
It says if two or more than two orbitals having the same amount of energy are unoccupied
then the electrons will start occupying them individually before they fill them in pairs. It is
a rule which depends on the observation of atomic spectra, which is helpful in predicting
the ground state of a molecule or an atom with one or more than one open electronic
shells.
The above configuartion can be represented as

1s22s22p63s23p64s23d6
Angular momentum and Magnetic Moment of the Atoms

Every electron has two kinds of magnetic moment; Orbital angular momentum and spin
angular momentum given by:

1⁄
𝑙 = (ℎ⁄2𝜋)(𝑙(𝑙 + 1)) 2

1⁄
𝑠 = (ℎ⁄2𝜋)(𝑠(𝑠 + 1)) 2 ……………………………………… 1

The coupling of the spin and orbital momentum results into total angular momentum 𝑗
given by
1⁄
𝑗 = (ℎ⁄2𝜋)(𝑗(𝑗 + 1)) 2 ……………………………………….. 2

𝑗 can have the values 𝑗 = 𝑙 + 𝑠, 𝑙 + 𝑠 − 1, 𝑙 + 𝑠 − 2 … … … … . |𝑙 − 𝑠|

The number of possible values of 𝑗 is equal to 2𝑠 + 1 or 2𝑙 + 1 whichever is smaller.

Coupling of l and s is magnetic leading to resultant magnetic moment 𝑗 which is a vector.
The direction of 𝑙 and s is the same as 𝑗 in absence of external field.

Orbital Magnetic Moment

Consider an electron in circular orbit of radius 𝑟 and velocity 𝑣. This constitutes a current
loop such that the current 𝑖 is given by
𝑒 𝑒𝑣
𝑖 = 𝑇 = 2𝜋𝑟 ……………………………………………………. 3

Where 𝑇 = 2𝜋𝑟⁄𝑣 is the periodic time of the electron motion. For a large loop the magnetic
moment is same as that of a magnetic dipole located at the centre of the loop. Let A be
loop area, the orbital magnetic dipole moment µ is
𝑒𝑣𝑟
𝜇 = 𝑖𝐴 = …………………………………………………………… 4
2

The direction of the magnetic dipole moment is perpendicular to the plane of the orbit.
But the angular momentum 𝑙 is

𝑙 = 𝑟 × 𝑝 where r is the position vector of the electron and p is the linear momentum and
are perpendicular thus

𝐼 = 𝑟𝑝 = 𝑚𝑒 𝑟𝑣 ………………………………………………………… 5

From 4 and 5
𝜇𝑖 𝑒 2𝜋𝑔1 𝛽𝑒
= 2𝑚 = …………………………………………………. 6
𝐼 𝑒 ℎ

ℎ⁄
2𝜋
Where 𝛽𝑒 = = 0.927 × 10−23 𝑎𝑚𝑝 − 𝑚2 is called the Bohr magneton and 𝑔1 = 1 called
2𝑚𝑒
𝜇𝑖
the orbital g factor. The ratio is independent of orbit size (r) and frequency 𝑓 since 𝑙 is
𝐼
quantized and equal to
1⁄
𝑙 = (ℎ⁄2𝜋)(𝑙(𝑙 + 1)) 2 then

1⁄
𝜇𝑖 = 𝛽𝑒 𝑔1 [𝑙(𝑙 + 1)] 2 …………………………………………….. 7

Equation 6 is written as
2𝜋𝑔1 𝛽𝑒 𝑙
𝜇𝑖 = − ………………………………………………………… 8
ℎ

Since the charge of the electron is negative

Spin magnetic moment is given as

2𝜋𝑔𝑠 𝛽𝑒 𝑠 1⁄
𝜇𝑖 = − = −𝑔𝑠 𝛽𝑒 [𝑠(𝑠 + 1)] 2
ℎ
Coupling of Angular Momenta

This is the process of combining two angular momenta to get a resultant momentum.
Consider a single electron with orbital angular momentum 𝑙 and spin angular momentum
𝑠 the total angular momentum is the vector sum of the two.

However, for two electrons with orbital momenta 𝑙1 and 𝑙2 and spin momenta s1 and s2
there are 6 ways of coupling the four vectors

𝑙1 𝑠1

𝑙2 𝑠2

𝑙1 𝑙2

𝑠1 𝑠2

𝑙1 𝑠2

𝑙2 𝑠1

Out of these the last two are negligible.

ll Coupling

This due to electrostatic interaction between orbital electrons.

Let 𝑙1 and 𝑙2 be the orbital angular momentum of two electrons

1⁄
𝑙1 = (𝑙1 (𝑙1 + 1)) 2 ……………………………………………………. 1
1⁄
𝑙2 = (𝑙2 (𝑙2 + 1)) 2 ……………………………………………………. 2

The two vectors add up to a resultant orbital angular momentum 𝐿 for the atom

𝐿 = 𝑙1 + 𝑙2 , 𝑙1 + 𝑙2 − 1, 𝑙1 + 𝑙2 − 2 … … … … . . |𝑙1 − 𝑙2 | …………….. 3

Let one electron be in 𝑝 and the other is in 𝑓 orbital,

𝑙1 = 1, 𝑙2 = 3 then L can have the values 4,3 and 2. The vectors have the lengths
1⁄ 1⁄
2
𝑙1 = (1(1 + 1)) =2 2

1⁄ 1⁄
𝑙2 = (3(3 + 1)) 2 = 12 2
 1⁄ 1⁄
𝐿 = (4(4 + 1)) 2 = 20 2

1⁄ 1⁄
𝐿 = (3(3 + 1)) 2 = 12 2

1⁄ 1⁄
𝐿 = (2(2 + 1)) 2 =6 2 ………………………………………………. 4
ss coupling

Arises from electrostatic interaction between electrons. The s vectors add up together.
But s can only have the values + 1⁄2 𝑜𝑟 − 1⁄2. For two electrons
1⁄ 1⁄
𝑠 = [1⁄2 (1⁄2 + 1)] = (3⁄4) …………………………………..
2 2
5

The two electrons can have same or opposite spins

𝑠1=+1⁄ , 𝑠2 = +1⁄2 ; 𝑆 = 𝑠1 + 𝑠2 = 1
2

1 1
Or 𝑠1=+1⁄ , 𝑠2 = −1⁄2 , 𝑆 = 2 − 2 = 0……………………………… 6
2

For 𝑛 electrons there are 2s+1 possible values given by

𝑛 + 1, 𝑛 − 1, 𝑛 − 3, … 2𝑜𝑟1 depending on whether n odd or even. For multi electron atoms

𝑆 = 𝑠1 + 𝑠2 + ⋯ … . , 𝑠1 + 𝑠2 + ⋯ . −1, 𝑠1 + 𝑠2 + ⋯ . . −2, … …. ………. 7

LS coupling

It is also called Russel-Sounders coupling. It is applicable to light atoms. For two electrons
𝑙1 and 𝑙2 couple to form a vector 𝐿 about which they are considered to be precessing
rapidly. Similarly 𝑠1 and 𝑠2 couple to form as resultant vector 𝑆. The S and L couple
together to form J

𝐽 = 𝐿 + 𝑆………………………………………………………………… 8
The values of J are

𝐽 = 𝐿 + 𝑆, 𝐿 + 𝑆 − 1, 𝐿 + 𝑆 − 2, … … … … |𝐿 − 𝑆| ……………………… 9

If there are more than 2 electrons, the LS coupling can be written symbolically as
(𝑠1 , 𝑠1 , 𝑠3 )(𝑙1 , 𝑙1 , 𝑙3 ) = (𝑆, 𝐿) = 𝐽

The interaction energy due to combinations are:

(𝑠1 , 𝑠2 ); 𝛤1 = 𝑎1 𝑠1 . 𝑠2 …………………………………………….. 10

(𝑙1 , 𝑙2 ); 𝛤2 = 𝑎2 𝑙1 . 𝑙2 …………………………………………….. 11

(𝑙1 , 𝑠1 ); 𝛤3 = 𝑎3 𝑙1 . 𝑠1 …………………………………………….. 12

(𝑙2 , 𝑠2 ); 𝛤4 = 𝑎4 𝑙2 . 𝑠2 ……………………………………………….. 13

In LS coupling 𝛤1 and 𝛤2 predominate. (𝑠1 , 𝑠2 ) and (𝑙1 , 𝑙2 ) precess rapidly around their
respective resultant L and S keeping the angles between each resultant vector and its
components constant. However, the angles (𝑙1 , 𝑠1 ) and 𝑙2 , 𝑠2 are not constant we thus
take their average values

𝛤3 = 𝑎3 𝑙1 . 𝑠1 ̅̅̅̅̅̅̅̅̅̅̅̅̅
𝑐𝑜𝑠(𝑙1 , 𝑠1 ) …………………………………………….. 14

𝛤4 = 𝑎4 𝑙2 . 𝑠2 ̅̅̅̅̅̅̅̅̅̅̅̅̅
𝑐𝑜𝑠(𝑙2 , 𝑠2 ) …………………………………………….. 15

But 𝑆 = 𝑠1 + 𝑠2

𝑆 2 = 𝑠1 2 + 𝑠2 2 + 2𝑠1 . 𝑠2
1
𝑠1 . 𝑠2 = 2 [𝑆 2 − 𝑠1 2 − 𝑠2 2 ]

1
𝑠1 . 𝑠2 = 2 [𝑆(𝑆 + 1) − 𝑠1 (𝑠1 + 1) − 𝑠2 (𝑠2 + 1)] ………………………… 16

From 𝐿 = 𝑙1 + 𝑙2

𝐿2 = 𝑙1 2 + 𝑙2 2 + 2𝑙1 . 𝑙2
1
𝑙1 . 𝑙2 = 2 [𝐿2 − 𝑙1 2 − 𝑙2 2 ]

1
𝑙1 . 𝑙2 = 2 [𝐿(𝐿 + 1) − 𝑙1 (𝑙1 + 1) − 𝑙2 (𝑙2 + 1)] ………………………… 17

Substituting the values of 𝑠1 . 𝑠2 and 𝑙1 . 𝑙2 in 10 and 11

 𝑎1
𝛤1 = 𝑎1 𝑠1 . 𝑠2 = [𝑆(𝑆 + 1) − 𝑠1 (𝑠1 + 1) − 𝑠2 (𝑠2 + 1)] …………….. 18
2

𝑎2
𝛤2 = 𝑎2 𝑙1 . 𝑙2 = [𝐿(𝐿 + 1) − 𝑙1 (𝑙1 + 1) − 𝑙2 (𝑙2 + 1)] ………………. 19
2

To obtain the values of 𝛤3 and 𝛤4 , the average values of the cosines must be evaluated

The average values of the cosines are written as

̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
cos(𝑙1 . 𝑠1 ) = cos(𝑙1 , 𝐿)cos(𝐿, 𝑆)cos(𝑆, 𝑠1 ) ……………………………… 20

̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
cos(𝑙2 . 𝑠2 ) = cos(𝑙2 , 𝐿)cos(𝐿, 𝑆)cos(𝑆, 𝑠2 ) …………………………….. 21

Substituting the average values of the cosines 14 and 15

𝛤3 = 𝑎3 𝑙1 . 𝑠1 ̅̅̅̅̅̅̅̅̅̅̅̅̅
𝑐𝑜𝑠(𝑙1 , 𝑠1 ) …………………………………………….. 14

𝛤4 = 𝑎4 𝑙2 . 𝑠2 ̅̅̅̅̅̅̅̅̅̅̅̅̅
𝑐𝑜𝑠(𝑙2 , 𝑠2 ) …………………………………………….. 15

𝛤3 = 𝑎3 𝑙1 . 𝑠1 cos(𝑙1 , 𝐿)cos(𝐿, 𝑆)cos(𝑆, 𝑠1 ) ……………………………… 22

𝛤4 = 𝑎4 𝑙2 . 𝑠2 cos(𝑙2 , 𝐿)cos(𝐿, 𝑆)cos(𝑆, 𝑠2 ) …………………………….. 23

Adding 22 and 23

𝛤3 +𝛤4 =𝑎3 𝑙1 . 𝑠1 cos(𝑙1 , 𝐿) cos(𝐿, 𝑆) cos(𝑆, 𝑠1 ) + 𝑎4 𝑙2 . 𝑠2 cos(𝑙2 , 𝐿)cos(𝐿, 𝑆)cos(𝑆, 𝑠2 ) .. 24

From 𝐿 = 𝑙1 +𝑙2 ; 𝑙1 = 𝐿 − 𝑙2 ;

𝑙1 2 = 𝐿2 + 𝑙2 2 − 2𝐿. 𝑙2

𝐿2 +𝑙2 2 −𝑙1 2
cos(𝐿, 𝑙2 ) = ……………………………………………….. 25
2𝐿𝑙2

𝐿2 +𝑙1 2 −𝑙2 2
cos(𝐿, 𝑙1 ) = ……………………………………………….. 26
2𝐿𝑙1

From 𝑆 = 𝑠1 + 𝑠2 we have

𝑠2 2 = 𝑆 2 + 𝑠1 2 − 2𝑆. 𝑠1
𝑆 2 +𝑠2 2 −𝑠1 2
cos(𝑆, 𝑠2 ) = ………………………………………………… 27
2𝑆𝑠1

𝑆 2 +𝑠1 2−𝑠2 2
cos(𝑆, 𝑠1 ) = ……………………………………………….. 28
2𝑆𝑠2
 (𝐿2 +𝑙1 2 −𝑙2 2 )(𝑆 2 +𝑠1 2 −𝑠2 2 ) (𝐿2 +𝑙2 2 −𝑙1 2 )(𝑆 2 +𝑠2 2 −𝑠1 2 )
𝛤4 + 𝛤3 = 𝐿𝑆𝑐𝑜𝑠 (𝐿, 𝑆) [[𝑎3 ] + [𝑎4 ]] ….. 29
4𝐿2 𝑆 2 4𝐿2 𝑆 2

𝛤4 + 𝛤3 = 𝐴𝐿. 𝑆 …………………………………………………………………………. 30

Where

(𝐿2 +𝑙1 2 −𝑙2 2 )(𝑆 2 +𝑠1 2 −𝑠2 2 ) (𝐿2 +𝑙2 2 −𝑙1 2 )(𝑆 2 +𝑠2 2 −𝑠1 2 )
𝐴 = [[𝑎3 4𝐿2 𝑆 2
] + [𝑎4
4𝐿2 𝑆 2
]]

From 𝐽 = 𝐿 + 𝑆 we have

𝐽2 = 𝐿2 + 𝑆 2 + 2𝐿. 𝑆

and making LS the subject we get

1 1
𝐿. 𝑆 = 2 (𝐽2 − 𝐿2 − 𝑆 2 ) = 2 (𝐽(𝐽 + 1) − 𝐿(𝐿 + 1) − 𝑆(𝑆 + 1)) ……………………… 31

But 𝛤4 + 𝛤3 = 𝐴𝐿. 𝑆
1
𝛤4 + 𝛤3 = 𝐴𝐿. 𝑆 = 2 (𝐽(𝐽 + 1) − 𝐿(𝐿 + 1) − 𝑆(𝑆 + 1)) …………………………………… 32

Equation 32 is the Lande interval rule which states that “the separation between pairs of
consecutive levels in a multiplet are proportional to the larger of the J values
characterizing the pair of the levels.

jj coupling

This occurs where the spin-orbit interaction of the electron is larger than the electrostatic
interaction between electrons. This is obtained by coupling the 𝑠 and 𝑙 of each electron to
resultant 𝑗 and then coupling the j vectors of the individual electrons to form a resultant 𝐽.
This occurs in atoms of large atomic number Z.

Considering two electron system we have;

𝐽 = 𝑗1 + 𝑗2 ………………………………………………………………… 33

J can have the values

𝐽 = 𝑗1 + 𝑗2 , 𝑗1 + 𝑗2 − 1, 𝑗1 + 𝑗2 − 2, 𝑗1 + 𝑗2 − 3, … … . . |𝑗1 − 𝑗2 |
 1
𝛤4 + 𝛤3 = 𝐴𝐿. 𝑆 = (𝐽(𝐽 + 1) − 𝐿(𝐿 + 1) − 𝑆(𝑆 + 1))
2

𝑎3
𝛤3 =
2
( 𝑗1 ( 𝑗1 + 1) − 𝑙1 (𝑙1 + 1) − 𝑠1 (𝑠1 + 1)) …………………………… 34
𝑎4
𝛤3 =
2
( 𝑗2 ( 𝑗2 + 1) − 𝑙2 (𝑙2 + 1) − 𝑠2 (𝑠2 + 1)) …………………………… 35

Term Symbols

These are designations of atomic states described by L and S. The general

representation of a term symbol is 2S+1L where L is the total orbital angular momentum
quantum number. For each value of L there exists a term designation as in atomic orbitals

Value of L 0 1 2 3 4 5 6 7 8 9 10
Term Designation S P D F G H I K L M N

S is the resultant spin quantum number of the atom and 2S+1 is the spin multiplicity.
The values of the multiplicity are as follows;

2S+1 value 1 2 3 4 5 6 7
Designation Singlet doublet Triplet Quartet Quintet Sextet Septet

For designations with multiplet level the value of J is given as a subscript

2S+1
LJ

where J is the total angular momentum quantum number of the atom and takes the
values

𝐽 = 𝐿 + 𝑆, 𝐿 + 𝑆 − 1, 𝐿 + 𝑆 − 2, … … … . |𝐿 − 𝑆|

Consider the term 4F. The value of L for term is 3 and 2𝑆 + 1 = 4 thus 𝑆 = 3⁄2. The
possible values of J are

𝐿 + 𝑆 = 3 + 3⁄2 = 9⁄2

𝐿 + 𝑆 − 1 = 3 + 3⁄2 − 1 = 7⁄2

𝐿 + 𝑆 − 2 = 3 + 3⁄2 − 2 = 5⁄2
𝐿 + 𝑆 − 3 = 3 + 3⁄2 − 3 = 3⁄2 = |𝐿 − 𝑆|

This implies that for the 4F there exists four multiplet levels:
4
F9/2
4
F7/2
4
F5/2
4
F3/2

Term Derivation from Electronic Configuration

LS Coupling

a) Terms of Non-equivalent atoms

These are electrons having different values of 𝑛 and 𝑙, for example

3s3p the values of 𝑙 are 0 and 1, 3s4s, the values of n are 3 and 4. Nonequivalent
electrons cannot have the 4 sets of quantum numbers the same thus the Pauli
Exclusion Principle is automatically satisfied.

The allowed values of quantum number L are obtained by summing the individual
angular momentum 𝑙𝑖 and the spin angular momentum 𝑠𝑖 to form S.

Example 1

Consider the 𝑝𝑓 electrons

For the p electron 𝑙2 = 1, 𝑙1 = 3

𝐿 = 𝑙2 + 𝑙1 , 𝑙2 + 𝑙1 − 1, 𝑙2 + 𝑙1 − 2, … … … |𝑙2 − 𝑙1 |

𝐿 = 4, 3,2

For each electron 𝑠 = 1⁄2 thus 𝑆 = 1⁄2 + 1⁄2 = 1, 1⁄2 − 1⁄2 = 0

𝑆 = 0,1

The states are

𝐿 = 4, 3,2, 𝐺, 𝐹 𝑎𝑛𝑑 𝐷

The possible multiplicities are; for 𝑆 = 0

2𝑆 + 1 = 1

For 𝑆 = 1,

2𝑆 + 1 = 3

The states will therefore be

1
D, 3D, 1F, 3F, 1G, and 3G

Equivalent Electrons

These are electrons with the same n and l. Using Pauli exclusion principle and the Breit
scheme. Consider two p electrons they must be differentiated by either ml or ms values.

For p electrons;

Case 1

Let

𝑙=1

𝑚𝑙 = −1,0, +1

(𝑚𝑙 )1 1 0 -1
2 1 0 1
1 0 -1 0
0 -1 -2 -1
(𝑚𝑙 )2

This yields the combinations

ML=+1,0,-1; MS=+1, 0,-1

By allowing ML values to be alike, then s must have opposite spins MS thus MS can only be
equal to zero

ML =2,1,0,-1,-2; MS =0
By allowing the 𝑚𝑠 values to be alike then the diagonal values are forbidden as they originate
from same 𝑚𝑙 thus violating Pauli exclusion principle. The ML in the lower left is a mirror
image of the upper right thus we eliminate one

(𝑚𝑠 )1 +1/2 -1/2

1 0 +1/2
0 -1 -1/2
(𝑚𝑠 )2

𝑀𝐿 = 1,0, −1 and 𝑀𝑠 = 1, −1

Case 2

If on the other hand we allow 𝑚𝑙 values to be alike the values 𝑀𝑠 = 1, −1 are forbidden by
Pauli Exclusion principle.

𝑀𝐿 = 2,1,0, −1, −2 and 𝑀𝑠 = 0

Comparing

𝑀𝐿 = 2,1,0, −1, −2 and 𝑀𝑠 = 0

𝑀𝐿 = 1,0, −1 and 𝑀𝑠 = 1, −1

𝑀𝐿 = 1,0, −1 and 𝑀𝑠 = 1, −1

Combining

i. ML=1,0,-1; MS=1,0,-1

But ML=+L, L-1, L-2………..-L

Thus L=1, and it’s a P term

S=1, Multiplicity (M)=2s+1=3

3P term

ii. ML=2,0,-2; MS=0

L=2, S=0; M=2S+1=1

It’s a 1D term

ML=0; MS=0; M=1

L=0

It’s a 1S term

Examples

Find the term symbols for:

1. 1S1

There is only I electron in S orbital 𝑙 = 0 + 𝐿

Thus it’s an S term

𝑆 = 1/2

𝑀 = 2𝑆 + 1 = 2
1
𝐽 = 𝐿 + 𝑆 = 0 + 2 = 1/2

Term Symbol is 2S1/2

2. 1s2 2s2 2p1

There still only one open shell electron.

1
𝑙 = 1 = 𝐿; 𝑠 = 2 ; 𝑀 = 2𝑠 + 1 = 2

Thus it’s a 2P term. But

1 3 1 1
𝐽 = 𝐿 + 𝑆 = 1 + 2 = 2;1 − 2 = 2

Thus there are two terms

2P and 2P1/2
3/2

3. 1s2 2s1 2p1

We have 2 electrons with 𝑙1 = 0, 𝑙2 = 1

𝐿 = 𝑙1 + 𝑙2 = 1; 𝑆 = 1,0

𝑀 = 2𝑆 + 1 = 3,1
This is a P term with multiplicities 3 and 1. (1P and 3P)

Term L S J=L+S Term Symbols

1P 1 0 1 1P
1
3P 1 1 2, 1, 0 3P 3P 3P
2, 1, 0

The number of microstates (N) of a system corresponds to the total number of distinct arrangements for
“e” number of electrons to be placed in “n” number of possible orbital positions.
𝑛!
𝑁 = 𝑒!(𝑛−𝑒)!

Consider the p orbitals, these comprise a set of 3 orbitals that can accommodate 6 electrons
thus 𝑛 = 6. Suppose in a given atom there are 2 electrons to be filled in the 3 p orbitals then
𝑒 = 2.
6!
𝑁 = 2!(6−2)! = 15

If one should consider an atom with multiple unoccupied orbitals, the total number of microstates will
equal the product of the microstates for the individual orbitals. Consider the configuration an s1p2.

For s1 n=2 and e=1

2!
𝑁 = 2!(2−1)! = 2

For p2 𝑁 = 15

Total number of microstates 𝑁𝑇 = 2 × 15 = 30

`
 ATOMIC SPECTRA

Spectra of Alkali Metals Atoms

These are elements in Group 1 of the periodic table. They include

Element Atomic Number (Z) Electronic Configuration

Lithum (Li) 3 1s22s1
Sodium (Na) 11 1s22s22p63s1
Potasium (K) 19 1s22s22p63s23p64s1
Rabidium (Rb) 37 1s22s22p63s23p63d104s24p65s1
Cisium (Cs) 55 1s22s22p63s23p63d104s24p64d105s25p66s1

They consist of filled shells and ns unfilled shell containing only 1 electron. The closed shells have
zero total orbital angular momentum and zero spin angular momentum. The atomic spectra is
produced through excitation of the valence electron to higher levels. The electron can be excited
to s,p,d,f etc orbitals. If we consider the Rb-37

Terms of Rb

Ground State Excited Excited Excited orbital Term

Configuration Orbital Configuration (n)
[Rb]365s s [Rb]36ns1 6,7…….. 2
S1/2
[Rb]365s p [Rb]36np1 6,7…….. 2
P1/2, 2P3/2
[Rb]365s d [Rb]36nd1 4,5…… 2
D5/2, 2D3/2
[Rb]365s f [Rb]36nf1 4,5…… 2
F5/2, 2F7/2,

For the states P,D and F, each level consist of 2 closely spaced components with different values
of 𝑗 value.

 The ground state 52S of Rb is about 3.6eV and the first excited state is 2 eV more negative
than that of Hydrogen.
 The second excite state 52D of Rb is about 1.12 eV more negative than 𝑛 = 4 for
Hydrogen
 For a given value of n, the energy is most negative for the smallest value of 𝑙 since the
electron spends more time near the centre of the atom.
 For Rb the dependence of the energy on 𝑙 makes 62S more negative than 52D and 42F
 For large radii subshell with large values of 𝑛 and 𝑙 dependence becomes less and the
energy of valence electron becomes close to that of the H atom.
The transition of electron from one energy level to another is governed by selection rule that
∆𝑙 = ±1

Energy Level Diagram for Rb-37

The allowed transitions between different energy levels give rise to a large number of lines which
can be grouped into 4 series.

i. Principal Series: Transition from 2P to normal 2S state. It can be observed in both

absorption and emission spectrum. The lines lie within the UV region except the last line
which lies in the visible light region. The strongest line in intensity corresponds to the
transition from 2P to lowest 2S states and it is called the resonance line (52P to lowest 52S)
ii. Sharp Series: Arises from transition from 2S to the lowest 2P state with lines within the
visible and the infrared regions
iii. Diffuse series: Arises from transitions from 2D to lowest 2P. lines lie within Visible and IR
regions
iv. Fundamental Series: Arises from transitions from 2F to lowest 2D and the lines within the
visible and the IR region.
 The sharp and the diffuse series have a common limit
 The difference between the limit of the principal series and the common limit of sharp
and diffuse series is equal to the first member of the principal series
  The difference between limit of the diffuse and fundamental series is equal to the first
line of the diffuse series.

Unlike the hydrogen spectra series, the spectral series for Alkali metals converge towards shorter
wavelength. However, the wavenumbers agree with equation for Hydrogen
1 1 1
= 𝑣̅ = 𝑅𝐴 𝑍 2 (𝑛′ 2 − 𝑛" 2 ) ………………………………………………………….. 1
𝜆 𝑒 𝑒

𝑅𝐴 𝑍 2
𝑇= …………………………………………………………………………………….. 2
𝑛𝑒 2

T is the spectral term. If non-intergral quantum numbers are used then

𝑛𝑒 = 𝑛 − 𝜇(𝑙)……………………………………………………………………………. 3

Where n is an integer and 𝜇 is a fraction and a function of 𝑙 called quantum defect. 𝑅𝐴 is the
Rydberg constant for element A. According to Rydberg-Ritz
𝛿(𝑙)
𝑛𝑒 = 𝑛 − 𝜇 − ......................................................................................... 4
𝑛2

𝑛 − 𝑛𝑒 is almost a constant in a given spectra series but slightly larger for the lowest term
𝛿(𝑙)
owing to Ritz correction . However, 𝜇(𝑙) is almost independent of n for a given 𝑙. The table
𝑛2
below shows the values of quantum defects in Rb

Term n=4 n=5 n=6 n=7

S - 3.195 3.154 3.144
P - 2.713 2.676 2.664
D 1.233 1.293 1.32 1.33
F 0.011 0.016 0.02 -

There is large departure of quantum defect from zero such that 𝜇 (𝑆) > 𝜇 (𝑃) >
𝜇 (𝐷)indicates penetration closer to the core of the atom.

For the F term, the configuration is generally hydrogen like thus less quantum defect. The
small dependence of 𝜇(𝑙) is due to polarization of the charge cloud of the core by the valence
electron. This polarization gives rise to further attraction towards the centre thus for small
values of n, 𝜇(𝑙) is greater since they are closer to the core.

The quantum defect is used to explain the increased binding energy of the electron. The
binding can also be explained in terms of shielding effect.

The net charge of the nucleus attracting the valence electron depends on the amount of
shielding of the nuclear charge by the core electrons. If there is complete shielding, the
effective charge would be +e (the charge of 1 proton). Incomplete shielding increases the
effective charge of nucleus to the valence electron. Therefore in place of assuming quantum
defect in principal quantum number spectral terms may be written in terms of Effective
nuclear charge. The term is thus given as:
𝑅𝐴 𝑍 2 𝑒𝑓𝑓
𝑇= ……………………………………………………………………………………….. 5
𝑛2

Fine Structure

Careful examination of the alkali metal spectra reveals the following:

1. Each member of the principal series consists of a pair of transitions called simple
Doublets. The difference in wavenumber of the components decreases rapidly
towards UV region
2. The sharp series members are all simple doublets of constant difference in
wavenumber
3. All members of diffuse series consists of compound doublets
4. The wavenumber difference of the first doublet in principal series is equal to the
sharp series doublet separation.

The slitting of the levels and hence the splitting of the lines is due to spin-orbit interaction
acting on the valence electron.

NB: All the energy levels of the valence electron except 𝑙 = 0 split into two.

Level 1: Corresponds to total angular momentum 𝐽 = 𝑙 + 1/2

Level 2: Corresponds to total angular momentum 𝐽 = 𝑙 − 1/2

Where 𝐽 = 𝑙 − 1/2 lies lower

The energies of the two levels are related by:

∆𝐸1 ∆𝐸2 𝑅 𝛼2 𝑍 4
∆𝑣̅ = (∆𝑇)𝑗=𝑙+1/2 − (∆𝑇)𝑗=𝑙−1 = − = 𝑛3𝐴𝑙(𝑙+1) …………………………….. 6
2 ℎ𝑐 ℎ𝑐

For a given element ∆𝑣̅ falls rapidly with increasing 𝑛 𝑎𝑛𝑑 𝑙 and increases with increase in
atomic number. To account for shielding effect Lande’ modified the equation 6 replacing Z
with 𝑍𝑖 2 𝑍0 2 and 𝑛𝑒 where 𝑍0 𝑒 is equal to the charge of the nucleus plus the closed shell of
electrons and 𝑍𝑖 𝑒 is the effective inner charge treated as a parameter.

The selection rules for transition are:

∆𝑆 = 0; ∆𝑙 = ±1; ∆𝑗 = 0, ±1

Origin of Principal Doublet

Originates from transitions from 2P to 2S.

1 3
For 2P level 𝑙 = 1; 𝑠 = 2 ; 𝑡ℎ𝑢𝑠 𝑗 = 2 𝑎𝑛𝑑 ½

1
For 2S level 𝑙 = 0; 𝑠 = 2 ; 𝑡ℎ𝑢𝑠 𝑗 = ½

The Doublet P splits into 2 levels while S does not split.

2
P3/2

2
P1/2

2
S1/2

The spacing of the doublet is governed by the splitting of the lowest 2P level. There are two
transitions and therefore two lines are observed.

NB: The difference in the wavenumber spacing between the doublets is due to 2P splitting.
As the value of n increases the splitting of the 2P level decreases. Therefore far large values
of n the splitting is negligible thus in the limit of the series only 1 line is observed. For the
same n value, the separation increases with increase in atomic number. For example, the
doublet separation for Na=2.49cm-1 while for Rb=237.6cm-1.

Origin of Sharp Doublet

Originates from transition from the 2S to the lowest 2P. Since the 2S level does not split, the
spacing between the lines is governed by the lowest 2P state since all the transitions
terminate.

2
S3/2

2
P3/2

2
P1/2
Origin of Diffuse Doublet

Originates from the transition from different excited 2D level to the lowest 2P. Each D and P
level splits into two levels with different j values due to spin-orbit interaction. From the
selection rules only 3 transitions are possible.

2
D5/2

2
D3/2

2
P3/2

2
P1/2

The expected transitions are:

Transition ∆𝑆 = 0 ∆𝑙 = ±1 ∆𝑗 = 0, ±1 Remark Intensity

2
D5/2 to 2D3/2 0 0 +1 Forbidden

2
D5/2 to 2P3/2 0 +1 +1 Allowed Strongest (p)

2
D5/2 to 2P1/2 0 +1 +2 Forbidden

2
D3/2 to 2P3/2 0 +1 0 Allowed Weakest (r)

2
D3/2 to 2P1/2 0 +1 +1 Allowed Second
strongest (q)
2
P3/2 to 2P1/2 0 0 +1 Forbidden

The results reveal that the splitting results into a triplet due to the 3 transitions. However, for large
values of 𝑛, the splitting of D levels may be too small for close pair of transitions (2D5/2 to 2D3/2 and 2D3/2
to 2P3/2) to be resolved. It is for this reason that the triplet is called a compound doublet. Similar
observations are made with the fundamental series.
Intensity Rules

1. For a change ∆𝑙(≠ 0) in the transition from one term to another, in LS coupling, the strongest
lines are those with ∆𝑗 with the same sign as ∆𝑙 and the intensity increases with increase in 𝑗
2. For a change ∆𝑙 ≠ 0, the lines with a sign of ∆𝑙 opposite to that of ∆𝑗 are the weakest while the
lines with ∆𝑗 = 0 have intermediate intensities.

Applying these rules to the diffuse series the strengths of the spectral lines are as shown in the table
below:

Transition ∆𝑆 = 0 ∆𝑙 = ±1 ∆𝑗 = 0, ±1 Remark Intensity

2
D5/2 to 2D3/2 0 0 +1 Forbidden

2
D5/2 to 2P3/2 0 -1 -1 Allowed Strongest

2
D5/2 to 2P1/2 0 +1 +2 Forbidden

2
D3/2 to 2P3/2 0 -1 0 Allowed weakest

2
D3/2 to 2P1/2 0 -1 -1 Allowed Second
strongest
2
P3/2 to 2P1/2 0 0 +1 Forbidden

Quantitative rules for relative intensities between two multiplets in LS coupling states that the sum of
the intensities of all transitions from an initial level or to a final level of a multiplet is proportional to the
statistical weight 2J+1 of that level. The constant of proportionality is common to all levels of a given
multiplet.

The diffuse fine structure involves three transitions with statistical weights as follows:

2 5
D5/2 = 6k = K (2 × 2 + 1 = 6𝑘)

2
D3/2 = 4k

Where k is constant
2
P3/2 = 4k’
2
P1/2 = 2k’

Let p,q and r represent the unknown intensities of the 3 allowed transitions and zero for the forbidden
transitions.

The ratio of the lines starting from 2D3/2 to those starting from 2P3/2 is
 𝑝 6𝑘 3
= = ………………………………………………………………………….. 7
𝑞+𝑟 4𝑘 2

The ratio of sum of lines ending in 2P3/2 to those ending in 2P1/2 is:

𝑝+𝑞 4𝑘 ′
𝑟
= 2𝑘 ′ = 2 ………………………………………………………………………… 8

Adding 1 to 7 and 8
𝑝 𝑞+𝑟 𝑝+𝑞+𝑟 5
𝑞+𝑟
+ 𝑞+𝑟 = 𝑞+𝑟
= 2 ………………………………………………………. 9

𝑝+𝑞 𝑟 𝑝+𝑞+𝑟
+ = = 3………………………………………………………….. 10
𝑟 𝑟 𝑟

Dividing 9 and 10
𝑝+𝑞+𝑟 𝑟 𝑟 5 1 5
𝑞+𝑟
× 𝑝+𝑞+𝑟 = 𝑞+𝑟 = 2 × 3 = 6 …………………………………….. 11

𝑟 = 5𝑞……………………………………………………………………………….. 12

𝑝 = 9𝑞……………………………………………………………………………….. 13

𝑝: 𝑞: 𝑟 = 9: 1: 5…………………………………………………………………… 14
Spectra of the Helium Atom

Helium has configuration 1s2. The 2 valence electrons are responsible for the observed optical spectra.
The two electrons have same 𝑛, 𝑙 𝑎𝑛𝑑 𝑚𝑙 and therefore spins are antiparallel (opposite) in ground state.
1 1
𝑙1 = 0; 𝑙2 = 0; 𝑠1 = + 2 ; 𝑠2 = − 2 ……………………………………………………… 1

𝐿 = 𝑙1 + 𝑙2 = 0; 𝑆 = 𝑠2 + 𝑠1 = 0; 𝐽 = 𝐿 + 𝑆 = 0 ………………………………… 2

The ground state is therefore 1S0.

If 1 of the electrons is excited to the 2p orbital, the configuration would be 1s12p1. In this state

𝑙1 = 0; 𝑙2 = 1; 𝐿 = 1 ……………………………………………………………………….. 3

So that this is a P state

The spins may be parallel or antiparallel so that;

1 1 1 1
𝑆 = + − = 0 𝑜𝑟 + = 1 ………………………………………………………….. 4
2 2 2 2

The multiplicity M is given by

𝑀 = 2𝑆 + 1 = 2 × 1 + 1 = 3 (𝑡𝑟𝑖𝑝𝑙𝑒𝑡) 𝑜𝑟 2 × 0 + 1 = 1(𝑠𝑖𝑛𝑔𝑙𝑒𝑡) …… 5

For the triplet the J values are

𝐽 = 𝐿 + 𝑆; 𝐿 + 𝑆 − 1 … … … |𝐿 − 𝑆|

𝐽 = 1 + 1 = 2; 1 + 1 − 1 = 1; 𝑎𝑛𝑑 1 + 1 − 2 = 𝐿 − 𝑆 = 0 ……………… 6

The possible terms for the triplet are 3P2, 3P1 and 3P0

For the singlet is 1P1

Ground State Excited State Possible n values for Terms

Configuration Configuration excited states
1s2 - - 1
S0
1s2 1sns 2,3,4…….. 1
S0, 3S1
1s2 1snp 2,3,4……… 1
P1, 3P2,1,0
1s2 1snd 3,4,5,6….. 1
D2, 3D3,2,1
1s2 1snf 4,5,6,……. 1
F3, 3F4,3,2

NB: the ground state only leads to a singlet while the excited states leads to a singlet and triplets.
According to Hund’s rule the triplets lie lower than the corresponding singlets. For the same n, the
energy term increases in order of nS, nP, nD, nF,…….
The lowest triplet state is 23S although the lowest singlet is 11S. The difference between 11S and 23S is
quite large (19.72ev) due to the tight binding closed shell in ground state.
X-Rays

X-rays are radiations in the electromagnetic spectrum of wavelength 10pm to 10 nm (10-12m to 10-9m).
Due to their high energies, X-rays have a refractive index of close to 1 for all materials. They are
produced in an X-ray tube.

The X-ray tube consists of an evacuated tube containing a cathode and an anode target. The cathode is
heated to high temperatures producing electrons. The electrons are accelerated towards the anode at
high speed to hit the target (Anode). When the fast moving electrons strike the target X-rays are produced
by 2 processes.

 Excitation of core electrons in the atoms of the target

 Deceleration of the electrons in the metal target

Deceleration gives a broad continuous spectrum while excitation gives sharp lines of specific energies
characteristic of the excitation energies of the target element.

The energy of an electron of charge e in dropping or accelerating through a potential difference V is eV.
ℎ𝑐
𝐸 = ℎ𝑣 = 𝜆
= 𝑒𝑉 ………………………………………………………………………………………. 1

ℎ𝑐 ℎ𝑐
𝜆= 𝐸
= 𝑒𝑉 ………………………………………………………………………………………………… 2

Before losing energy through excitation an electron loses some of its energy through collision with
atoms of the target thus the temperatures of the target increase. As a result λ is the minimum possible
wavelength for the X-rays produced.
The X-ray spectrum therefore has a cut off wavelength and continuum due to deceleration of electrons.
The electrons strike off electrons from the target. The vacancy created is filled by higher energy level
electrons leading to emission of photons of energy equal to the energy difference between the two
levels. Thus the wavelength of the photon is specific.

Suppose an electron in the K-shell is ejected, an electron from L,M,N…….will make a radiative transition
filling the hole in the K shell. The emission spectrum results into a series depending on the origin of the
vacancy. Lines originating from a vacancy in K shell are called 𝐾𝛼 , 𝐾𝛽 , 𝐾𝛾 , … .. arising from the
transitions L-K, M-K, N-K ……. The vacancies created in L,M,N shells are also filled by transitions from
higher levels thus K series is accompanied by L, M,N series which are weaker.

Depending on their energies X-rays are classified as Hard (high energy) e.g the K series or soft X-rays e.g.
the L series.
If one electron is removed from a closed subshell/orbital, the allowed value of the spin, orbital and total
angular moment for the remaining electrons is the same as that of one electron that can be used to fill
the hole left.

Therefre the states np1, nd1 are the same as that of np5 and nd9 respectively. It imlpies that n,l and j of a
subshell in which an electron is missing are identical with those of an electron that can be used to fill the
subshell. Since only 1 electro is missing from the subshell, then 𝑠 = 1/2 and Multipilcity is 2.

The energy levels shown are for different vaues of n although for each value of n there n-1 values of 𝑙
and for each value of 𝑙 there are 2 values of j corresponding to

𝑗 = 𝑙 + 1/2 and 𝑗 = 𝑙 − 1/2

Example

For L shell 𝑛 = 2
𝑙 = 0,1
1 3 1
𝑗 = 2 ; 𝑓𝑜𝑟 𝑙 = 0 𝑎𝑛𝑑 𝑗 = 2 𝑎𝑛𝑑 2 𝑓𝑜𝑟 𝑙 = 1

Thus each n is split into further 2n-1 components. In x-rays, shells are designatged by letters from n=1 to
n=7 as K,L,M,N,O,P Q and the levels in each shell by roman numerals in terms of increasing 𝑙 or 𝑗 for the
same 𝑙 value

𝑛 𝑙 𝑗 Designation State
1 0 1/2 K 1s1/2
2 0 1/2 Li 2s1/2
2 1 1/2 Lii 2p1/2
2 1 3/2 Liii 2p3/2
3 0 1/2 Mi 3s1/2
3 1 1/2 Mii 3p1/2
3 1 3/2 Miii 3p3/2
3 2 3/2 Miv 3d3/2
3 2 5/2 Mv 3d5/2

The transition of electrons in X-rays follows the transition rules ∆𝑙 = ±1; ∆𝑗 = 0, ±1.

Not all transitions are allowed. For example transition from Li to K is not allowed since ∆𝒍 = 𝟎. The
transitions Lii to K and Liii to K are allowed and named 𝑲𝜶𝟏 𝒂𝒏𝒅 𝑲𝜶𝟐 respectively based on their
intensities.

Dependence of Position of Lines on Atomic Number

The wavelength of chracteristic X-ray lines decreases with increase in Z thus the frequency and the
energy increase. This is due to increase on binding energy of the electrons with increasing number of
protons in the nucleus.

The electron energy for a given energy level is given by

ℎ𝑐𝑅𝑍 ∗2
𝐸𝑛𝑙 = 𝑛2
………………………………………………………………………………………………. 3

Where 𝑍 ∗ is the eefective nuclear charge given by 𝑍 ∗ = 𝑍 − 𝜎𝑛𝑙 and 𝜎𝑛𝑙 is the screening constant. The
term value is

𝐸𝑛𝑙 𝑅𝑍 ∗2
𝑇= ℎ𝑐
= 𝑛2
……………………………………………………………………………………………….. 4
For an emission line, thewavenumber in cm-1 is

1 1 1
𝑣̅ = = 𝑅𝑍 ∗2 ( − ) ……………………………………………………………………………. 5
𝜆 𝑛𝑓 2 𝑛𝑖 2

1 1
Letting (𝑛 2 − 𝑛 2) = 𝑎
𝑓 𝑖

1
𝑣̅ = 𝜆 = 𝑅𝑍 ∗2 𝑎 ……………………………………………………………………………………………. 6

𝑣̅
√ = 𝑍 ∗ √𝑎 = √𝑎(𝑍 − 𝜎𝑛𝑙 ) ………………………………………………………………………….. 7
𝑅

𝑎 is the same for similar lines of all elements and 𝜎 is approximately equal for all lines of a given series.
E.g. for all K line of all elements. Equation 7 is the Mosley Law which helped in identifying missing
elements I the periodic table. For 𝐾𝛼 line 𝑛𝑓 = 1 and 𝑛𝑖 = 2 thus 𝑎 = 0.866, 𝜎 ≈ 1 𝑎𝑛𝑑 7.4 for K and L
lines respectively.

For K series

𝑣̅
√ = 0.866(𝑍 − 1)
𝑅

1
𝑣̅ = 𝜆 = 0.8662 × 109737(𝑍 − 1)𝑐𝑚 −1

1 10−4 𝑐𝑚
𝜆= =
𝑣̅ 8.23×(𝑍−1)2

X-Ray Emission (Doublet) Spectra

The separation between adjacent X-ray terms of the same principal quantum number is referred to as
an X-ray Doublet. The intervals that correspond to differences between levels with the same n, l and s
but different j are called spin doublets or regular doublets.

The frequency interval remains constant across the spectrum of the same element but increases very
slowly with increase in Z. Examples of Spin doublets are

𝐿𝑖𝑖 𝑎𝑛𝑑 𝐿𝑖𝑖𝑖

𝑀𝑖𝑖 𝑎𝑛𝑑 𝑀𝑖𝑖𝑖

𝑀𝑖𝑖𝑖 𝑎𝑛𝑑 𝑀𝑖𝑣

The irregular or screening doublets are pairs of levels with the same n and 𝑗 but their 𝑙 differs by 1.
Examples are

𝐿𝑖 𝑎𝑛𝑑 𝐿𝑖𝑖

𝑀𝑖𝑖𝑖 𝑎𝑛𝑑 𝑀𝑖𝑣

𝑀𝑖 𝑎𝑛𝑑 𝑀𝑖𝑖

The energy of a given level due to coulomb interaction of an electron with the nucleus and energy level
is given by;

ℎ𝑐𝑅𝑍 ∗2 ℎ𝑐𝑅(𝑍−𝜎1)2
𝐸𝑛 = 𝑛2
= 𝑛2
………………………………………………………………………………………. 8

Where 𝜎1 is the screening constant depending on value of 𝑙. Taking into account relativistic effect and
spin –orbit interaction the position of the energy levels may be expressed like the hydrogen.

ℎ𝑐𝑅(𝑍−𝜎1)2 ℎ𝑐𝑅(𝑍−𝜎2)2 3 1
𝐸𝑛𝑙𝑗 = − + [ − 𝑗+1/2] ……………………………………………………… 9
𝑛2 𝑛2 4𝑛

Since the screening constant is an average over ranges of effective Z, there are different creening
constants for expression with different powers of Z.

The term value is:

𝑅(𝑍−𝜎1 )2 𝑅(𝑍−𝜎2)2 3 1
𝑇𝑛𝑙𝑗 = + [ − ] ………………………………………………………………………. 10
𝑛2 𝑛2 4𝑛 𝑗+1/2

The Doublet separation is given as:

𝑅𝛼 2 (𝑍−𝜎2)4
∆𝑇 = 𝑛3𝑙(𝑙+1)
…………………………………………………………………………………………………. 11

Thus the energy difference is independent of Z but proportional but depends on 𝜎2 which increases as
move to subshells further from the nucleus. For 𝐿𝑖𝑖 = 3.5, 𝐿𝑖𝑖𝑖 = 8.5, 𝑒𝑡𝑐. The first term in equation 10
predominates thus we can ignore 𝛼 2 so that

𝑅(𝑍−𝜎1)2
𝑇= 𝑛2
……………………………………………………………………………………………………………. 12

For the two levels a and b

𝑅(𝑍−𝜎1)𝑎
√𝑇𝑎 = √𝑅 𝑛
………………………………………………………………………………………………… 13

𝑅(𝑍−𝜎1 )𝑏
√𝑇𝑏 = √𝑅 𝑛
………………………………………………………………………………………………… 14

Since a and b involve different orbits 𝜎1 is different in both cases

 √𝑅 √𝑅
∆√𝑇 = √𝑇𝑎 − √𝑇𝑏 = [𝜎1𝑏 − 𝜎1𝑎 ] = ∆𝜎1 ………………………………………… 15
𝑛 𝑛

Continuous X-Ray Emission

This is due to slowing down of the electron movement as it strikes the target in the coulomb field of the
nucleus. The continuous X-ray has a sharp limit 𝜆0 on the lower wavelength side whose value depends
on the acceleration potential of the X-ray tube.

ℎ𝑐
𝜆0 = 𝑒𝑉 ……………………………………………………………………………………………… 16

X-Ray Absorption Spectra

When a beam of X-rays passes through a sample, the intensity of the X-rays becomes weaker due to
absorption and scattering. This occurs due to absorption of X-rays by the material. This occurs through a
single process. The X-ray photon knocks out electron from a shell and the energy of the absorbed
photon is transformed into kinetic energy of the electron plus potential energy equal to the binding
energy of the electron (Energy required to eject the electron from the shell).

X-rays of longer wavelength (lower energy knock out electrons from the outer shell. With increasing
energy just a fraction of the X-ray energy is required to knock off these electrons causing a reduction in
the rate of absorption until the X-ray energy is large enough to knock electrons from next inner shell.
Once this is reached, a sharp increase in absorption is obtained.

This results to sharp discontinuities of the absorption cross section (µ) with wavelength called the
absorption edge which corresponds to the photons critical energy.

The absorption edges are labeled K edge, L edge, M edge etc. From the observed absorption Edges the
binding energies can be calculated.

Apart from the edge there general fall min absorption due to dependence of the absorption coefficient
with λ given by:

𝜇 = 𝑘𝜌𝜆3 𝑍 3 where k is a constant and 𝜌 is the density of the material. The wavelength of the absorption
edge is defined in terms of orbital energy
ℎ𝑐
𝜆𝑘 = 𝐸
𝑘

The absorption edge exhibits fine structure of the core state.

Atoms in External Fields