Faculty of Electrical Engineering

Department of Telecommunications
1st year Common core Engineers
Structure of Matter IST 1.4

Chapter III: Electronic structure of the atom

1. Corpuscle wave duality:

a. Wave aspect of light:
It is accepted that light is a combination of electric and magnetic fields propagating in space
with a wave movement. These electromagnetic or light waves propagate in space at a constant
speed C (speed of light) equal to 3.108 ms-1. Each of its waves is characterized by a
𝟏
̆=
wavelength λ or its wave number 𝝂
𝝀

The period T is the time after which the wave repeats itself identical to itself. The number of
wavelengths traveled per second and the frequency ν of light is given by:

𝒄 𝟏
𝝂= =
𝝀 𝑻

Figure III.1.Electromagnetic spectrum

b. Corpuscular appearance of light:

Each component of white light is a light radiation characterized by a very specific color
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(consisting of an infinity of colors; red, blue, etc.) and each color corresponds to an energy, a
frequency and a wavelength.
In its corpuscular aspect, light radiation can be considered as consisting of very small particles
called photons carrying light energy E according to the relationship: E=hυ.
With: h: Planck constant (6.626 10-34 d.s)
E: Light energy transported by radiation in Joule
υ: Frequency of radiation in Hz.

c. Photoelectric effect:
The photoelectric effect was discovered by Hertz around 1885. If we illuminate a metal plate
with monochromatic light of frequency higher than the threshold frequency, the excess energy
compared to the characteristic energy of the metal E0= hυ0 is dissipated in the form of kinetic
energy taken by the electrons (Figure III.2).
 Only light of frequency υ > υ0 determines an emission of electrons;

 If a photon of energy (E=hυ ≥ E0= hυ0 ) is absorbed, the emitted electron will reach a
kinetic energy: Ec= E - E0.

Figure III.2. The emission of electrons from a metal plate

2. Emission spectrum of the hydrogen atom

The spectrum of the hydrogen atom is made up of monochromatic radiations of well-defined
wavelengths λ (Figure III.2). Experiment has shown that the emission spectrum of the
hydrogen atom has a large number of lines in the ultraviolet, visible and infrared. The first
lines studied are located in the visible domain. They belong to the "Balmer series".

Analysis of the electromagnetic radiation emitted by excited hydrogen atoms shows that it is
made up of four light lines.

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 Figure III.3. Spectrum of the hydrogen atom

Figure III.4. Diagram of an electronic transition.

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 a. The Balmer-Rydberg empirical relationship:
Rydberg then proposed an empirical equation which allows us to relate the wavelength λ to the
𝟏 𝟏 𝟏
energy levels n by the relation: = 𝑹𝑯 ( − )
𝝀 𝟐𝟐 𝒏𝟐𝟐
With :

n:number of the line which takes the successive values 3, 4,5,6,..;

λ: corresponding wavelength
RH: Rydberg constant for hydrogen, found experimentally =1.1 107 m-1.

The seven visible lines observed constitute the visible of white light and form the Balmer
series for which n1= 2 and n2 >2.
b. Concept of series of lines:

Ritz generalized Rydberg's empirical relation to find the wavelengths of all the lines of the
different series observed according to the following relationship:
𝟏 𝟏 𝟏
= 𝑹𝑯 ( 𝒏𝟐 − 𝒏𝟐𝟐
)
𝝀 𝟏
With: n1 and n2 positive integers (n1>0 and n2>n1).

Exploration of the entire spectrum shows the existence of other series of lines on either side of
the domain visible in this table:
Table III.1.Hydrogen spectrum series, transitions and corresponding spectral domain.

Series Transition Spectral domain

lyman n1= 1 and n2 ≥2 Ultraviolet
Balmer n1= 2 and n2 ≥3 Visible
Paschen n1= 3 and n2 ≥4 Infrared
Brackett n1= 4 and n2 ≥5 Infrared
Pfund n1= 5 and n2 ≥6 Infrared

3. Bohr's atomic model: hydrogen atom

a. Radius of the hydrogen atom:
Hydrogen is made up of a nucleus of charge (+e) and an electron of charge (-e) separated by a
distance r (diagram below). The electron describes a circular trajectory with a speed v, while
the relatively heavy nucleus remains practically fixed.

Fa: The attractive force given by:

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 𝑲𝒆𝟐 𝟏
Fa = ,k=
𝒓𝟐 𝟒𝝅𝜺𝟎
𝒎𝒗𝟐
Fc:The centrifugal force Fc =
𝒓
According to Bohr's first postulate, the system is in equilibrium:

According to Bohr's second postulate describing the quantification of orbital angular

momentum, we have:

Figure III.5. Schema of the atom

Combining equation (1) with (2) leads to the expression for the radius of the orbit: and as, h, π,
k, m and e are constant then r only depends on the value of the positive number n called the
principal quantum number:

For n = 1, rn=r1= 0.53 Å : first Bohr radius for the hydrogen atom which we note a0.

b. Energy of the hydrogen atom:

The total energy Et of the system considered is the sum of the potential energy Ep and the
kinetic energy Ec: Et= Ep+ Ec ………(4)

With :

According to equation (1, 2, 3, 4, 5 and 6) the total energy of the electron in the orbit depends
only on n. It is therefore quantified and can only take a few values
particular in accordance with the expression:

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For n=1, E1= -13.6eV. This value represents the ground state energy of the atom Hydrogen, hence:

c. Hydrogenoid ion spectrum:

Hydrogenoid ions are cations that have a single electron and Z protons.
Example : He+, Li2+, ….
Calculation of the radius and energy of the electron of a hydrogenoid ion in an n orbit results in
the following expressions:

The Ritz relation for hydrogenoids becomes:

𝟏 𝒁𝟐 𝒁𝟐
= 𝑹𝑯 ( 𝟐 − 𝟐 )
𝝀 𝒏𝟏 𝒏𝟐

a. Bohr's postulates:

1st postulate: the electron describes stationary circular orbits around the nucleus, i.e. the
energy remains constant.

2nd postulate: for the associated wave to find itself in phase after one orbit of radius r, it is
𝐧𝐡 𝟐𝛑𝐫
necessary that n𝜆= 2πr (n: integer) hence V= but 𝜆 = SO :
𝟐𝛑𝐦𝐫 𝐧
𝒉 𝒏 𝒏 𝟏 𝒉 𝟏
V= . gold . hence V = .
𝒎 𝟐𝝅𝒓 𝟐𝝅𝒓 𝝀 𝒎 𝝀

𝒉
SO: λ=
𝒎𝒗
3rd postulate: When the atom goes from an energy level En to an energy level
lower En' (En>En'), there is emission of electromagnetic radiation of frequency ν

ΔE = h𝝂 = Em- En

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 Or: n ˂ m
 When the electron goes from level n to level m, it is an absorption, and the energy:
Δ𝐸=ℎν= Em- En
 When the electron passes from level m to level n, it is an emission, and the energy:
Δ𝐸=ℎν= En-Em

4. Quantum mechanics (wave mechanics):

Bohr’s model based on classical mechanics does not correctly describe the behavior of atoms.
Indeed, classical physics, which allows us to know the evolution over time of a system on a
macroscopic scale, proves insufficient to account for phenomena on the atomic scale. At the
beginning of the 20th century, a new mechanical theory, called quantum mechanics capable of
studying microscopic systems, was born.

a. Hypothesis of Louis de Broglie:

According to Louis de Broglie, the movement of any material particle can be compared to a
wave process. The length of the wave associated with this particle is called the "wave of
broglie". It is given by the relation
ℎ
λ= .
𝑚𝑣
b. Heisenberg uncertainty principle:

According to Heisenberg's uncertainty principle, it is impossible to precisely determine the

position of particule and its a quantity of movement (or impulse).
The uncertainty relation obeys the relation:

Δx is the uncertainty on the position

Δpx the uncertainty in the a quantity of movement
(momentum).

c. Schrödinger's equation:
Quantum mechanics describes matter as a set of atomic nuclei around which electrons
orbit, which are themselves explicitly described by their probability of presence at a point
and represented by wave functions. The foundations of quantum computation were laid in
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1925 by Heisenberg, Born and Jordan, and finalized in 1926 by Schrödinger and his
famous equation (III.1), whose formalism makes it possible to rigorously describe the
microscopic nature of matter.
ĤΨ=EΨ (III.1)
This is the fundamental principle of quantum mechanics.

With :

E: total energy of the electron, called eigenvalue

Ψ: wave function called eigenfunction

H: is called the Hamiltonian operator

m: mass of e-: Potential energy operator

𝝏𝟐 𝝏𝟐 𝝏𝟐
𝛁= + + The Laplacian
𝝏𝒙𝟐
𝒌 𝝏𝒚𝟐
𝒌 𝝏𝒛𝟐
𝒌

d. Solutions of the Schrödinger equation:

A hydrogenoid atom is an atom consisting of a nucleus with a positive charge (+Ze)
surrounded by a single electron of mass me and charge (–e). The nucleus of the atom with a
very large mass compared to that of the electron is assumed to be fixed. The Schrödinger
equation is written for a hydrogenoid atom:

−𝒉𝟐
( ∆𝟐 + 𝑬𝒑 )𝛹 = E𝛹
𝟖 𝝅𝟐 𝒎

With: (x, y, z) depends on Cartesian coordinates x, y, z.

The solutions depend on three parameters n, l, m which are integers. The parameters must
obey the conditions: n>0 0 ≤ l ≤ n-1 -l ≤ m ≤ +l

5. Quantum numbers:

5.1. Principal quantum number, n:

It is a positive integer: n= 1, 2, 3…etc. It defines the electronic layer.

Layers are designated by a symbol:

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 Table III.2.Values of n and corresponding layer

Value of n 1 2 3 4 5
Layer/orbit K L M N O

5.2. Secondary (azimuthal) quantum number l: This number characterizes the sub-layer
(or sublevel) occupied by the electron. It defines the shape of the volume in which
the electron is located, i.e. the shape of the orbitals. l is an integer 0≤ l ≤ n-1: the
values of l and corresponding sublayers :
Table III.3. The values of l and the corresponding sublayer.

Value of l 0 1 2 3 4
Sublayer/orbital S p d f g

5.3. Magnetic quantum number m: This number defines the number of orientations in
space that the electron can take when subjected to the action of a magnetic field. It
characterizes the quantum box occupied by the electron. –l ≤ m ≤ +l :

Table III.4. The values of m and the corresponding quantum boxes.

Value of m 0 -1, 0, 1 -2, -1, 0, 1, 2 -3, -2, -1, 0, 1, 2, 3

Presentation of boxes

5.4. Spin quantum number S: In addition to n, l, m the state of an electron must be

characterized by a fourth number linked to the electron's own state; this number is
The spin quantum number S has two values:
S= +1/2 (↑) and S= -1/2 (↓)

Geometric shape of the different atomic orbitals

Orbital S:
orbitals ( S) are characterized by l=0, m=0, all (S) or (nS) orbitals have spherical
symmetry, as the electron's probability of presence varies equally in all directions around
the nucleus
Orbital P :
for l=1, we have m=-1,0,+1, three P orbitals we refer to as P orbitals PX, PY and PZ.
having the same but each elongated on one of the three perpendicular axes.

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 Orbital d :
if l=2, m=-2,-1,0,+1,+2 :so we have five d orbitals :

6. Electronic configuration of elements:

The distribution of electrons within the various atomic orbitals (Layers and sub-layers), stated in
order of increasing energy, is called the electronic configuration of the atom. The filling of the
quantum or atomic orbital boxes must imperatively respect the following four rules.

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  Stability rule: When the atom is in the ground state, the electrons occupy the most stable
energy levels corresponding to the lowest energy.

 Pauli's rule: exclusion principle: Two electrons of the same atom cannot have all their
four quantum numbers identical. In other words, in a quantum box, the electrons must have
anti-parallel spins.
 Hund's rule: In the same sub-layer, the most stable configuration (i.e. that of the ground
state) is obtained when the number of electrons with identical spins is maximum.
We first occupy a maximum number of empty orbitals by an electron with spin +1/2 (↑).
Subsequently, to the extent of the remaining electrons available, a second electron (of spin -
1/2 (↓)) is added to each orbital.
 Klechkowski rule:
The order of filling the sub-layers obeys Klechkowski's rule, illustrated in the following
diagram:

The order of filling according to increasing energy: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d

6p 7s 5f 6d 7p……..

Examples: Electronic structure or electronic configuration in the ground state:

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O (8 electrons to place): 1s2 / 2s2 2p4 → core electrons / valence electrons
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Co: 1s2, 2s2, 2p6, 3s2, 3p6 / 4s2, 3d7

It is preferable to write: 1s2, 2s2, 2p6, 3s2, 3p6 /3d7, 4s2

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Examples: Exceptions to Klechkowski's rule.

- Chrome: 24Cr: 1s2, 2s2, 2p6, 3s2, 3p6 /3d5, 4s1 and not: 3d4, 4s2

- Copper: 29Cu: 1s2, 2s2, 2p6, 3s2, 3p6 /3d10, 4s1 and not: 3d9, 4s2

Note: 1s 2 2s2 2p4

 Underlined numbers indicate the number of layers, n = 1, 2, 3, …

 The letters s, p, d, f, …indicate the sub-layers.

 The exponent number indicates the number of electrons in the layer considered

Screen Effect: Slater's rules are a set of (empirical) rules used to evaluate the effective
nuclear charge. In a multi-electron atom, the effective charge perceived by each electron is:
Z*= Z-σ.
Where Z is the real nuclear charge and σ represents the screen effect produced by electrons
closer or as close to the nucleus.
The screen effect σj on the electron j is the sum of the screening effects σj→i exerted on
electron j by any other electron i, taking into account the situation of electron j.

According to Slater the effects of other electrons are determined by the following rules:

 Each other electron in the same group as electron j exerts a screening effect
equivalent to 0.35 (electronic charges), with the exception of group 1s for
which the screening of one electron on the other is 0.30.

 An electron j of an ns np group undergoes a screen of 0.85 by each electron of

principal quantum number (n - 1), as well as a screen of 1.00 by each electron of
lower principal quantum number.

 An electron j of a group nd or nf undergoes a screening of 1.00 by each electron of

a lower group, either with a lower value of n, or with the same value of n as
electron j and a lower value of the 1.

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Table III.5. Slater's rule (screening values)

electron j/electron i 1s 2s 2p 3s 3p 3d 4s 4p 4d
1s 0.30
2s 2p 0.85 0.35
3s 3p 1 0.85 0.35
3d 1 1 1 0.35
4s 4p 1 1 0.85 0.85 0.35
4d 1 1 1 1 1 0.35

Example: The chlorine (Cl) has Z=17 protons and therefore 17 electrons, and has the
electronic configuration: 1s2 2s2 2p6 3s2 3p5.
In this example we study the electrons of valence (i.e. belonging to the last electronic layer,
here 3s2 3p5):
Thus, the effective charge for each electron in the 3s or 3p sub-layer will be:
Z*= Z-σ
With a screening constant σ due to all other electrons in the 3s/p layer and lower layers. There
are 7 electrons in the 3s/p layer, 1 electron in the 3s or 3p layer will therefore be screened by
the 6 other electrons in this same layer, as well as that of the 8 electrons in the 2s/2p layer
and of the 2 electrons of the 1s layer.
The screen constant σ is therefore:
𝜎 = 6. 𝜎3𝑠,3𝑝+ 8. 𝜎2𝑠,2𝑝+ 2.𝜎1𝑠= 6.0.35 + 8.0.85 + 2.1 = 10.9

Which gives an effective charge of: Z*=17-10.9 = 6.1

Dr C.A. BERREKHCHI BERRAHMA

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