III.

Associated wave function :

1. Standing wave :
A standing wave is a wave that vibrates but does not move

Wall Wall
Node

Antinode
2. Wave function and associated wave amplitude function:

In wave mechanics, an electron located at a point with coordinates (x, y, z) at

time t is described by a function Ψ (x, y, z, t) known as the “wave function”
which represents the amplitude of the associated wave.
The wave function is a fundamental concept in quantum mechanics. It allows us
to describe the state of a particle, such as an electron or a photon, in space and
time. The wave function is a complex function and the square of its value at a
point in space and time gives the probability of finding the particle at that point.

 𝐱, 𝐲, 𝐳, 𝐭 =  𝐱, 𝐲, 𝐳 𝐬𝐢𝐧 𝟐𝛑𝐭

 𝐱, 𝐲, 𝐳 : associated wave amplitude function.

sin 2t : sinusoidal time function.

If the wave is a wave standing, the wave function only takes into account the
amplitude part, and the temporal part becomes meaningless.
 IV. The Schrödinger equation
In 1926, Erwin Schrödinger, starting from the matter waves of Louis de Broglie,
postulated a wave equation to describe a particle, in particular an electron.

The Schrödinger equation is a second-order

differential equation that describes the evolution of
Ĥ() = E
a quantum system in time. It is a wave equation Simplified formula
that describes the behavior of a wave function, ^  h2 
which is a mathematical function that describes the H    2 .  Ep
state of a quantum system.  8 m 
Hamiltonian operator
In quantum mechanics, the Hamiltonian operator
m : The mass of the electron
is used to describe the evolution of a system in
Ep : The potential energy operator
time. E : The total energy of the electron
called an eigenvalue
Is the Laplacian Ψ : The wave function called an
eigenfunction solution of the
 2  2  2 Schrödinger equation.
   2  2
x 2
y z
 h2  Developed
  2 .  Ep   E  formula
 8 m 
 Exemple in quantum mechanics:
Particle in a box or one-dimensional potential well
Application example:
Calculate the energy difference in joules, electronvolts and kJ/mol, between the
levels:
(a) n = 3 and n = 1,
(b) n = 7 and n = 6 of an electron in a box of length 1.50 nm.
Given: me = 9.110-31 kg. h = 6.6210-34 J.s
 V. Physical significance of the wave function:
1. The probability of finding
The probabilistic interpretation of the wave function was introduced by Max Born
in 1926.
Born proposed that the square of a particle's wave function represents the
probability of finding the particle at a given location. dP = 2 (x,y,z) dx dy dz

Erwin Schrödinger, the creator of the Schrödinger equation, originally proposed

that a particle's wave function represents the physical reality of the particle.
However, he later accepted Born's probabilistic interpretation.
But some physicists, such as Albert Einstein, found this interpretation difficult to
accept. However, the probabilistic interpretation has been confirmed by numerous
experiments, and it is today the basis of quantum mechanics.
 d
M1

M2

The probability of finding the electron in the volume  is given by the relation :

𝐏 = ම  𝟐 𝐝

The probability density of finding the electron at a point M (x, y, z)

The classical notion of position is At point M1, the probability of finding the
therefore replaced by the notion electron is higher than at point M2. Therefore,
of probability of finding or the probability decreases as M moves away
probability density of finding. from the nucleus.
2. normalization condition:

The normalization condition is a necessary condition for the wave function to be

physically meaningful.
The normalization condition for the wave function of an electron in a hydrogen
atom is expressed as:

We say that the wave function Ψ is normalized.

The wave function must also satisfy certain

mathematical properties:
• Continuity
• Uniformity.
•  (x, y, z) 0 when x or y or z  
The Universe is divided into an
infinity of volume elements.
 VI. Solution of Schrödinger equation :
The choice of Cartesian coordinates to solve the Schrödinger equation is not well-
suited due to the spherical symmetry of the atom; therefore, spherical coordinates
r, θ, φ are selected.

The resolution is done by

putting the function in the form
of a product of two functions :

Finding probability in spherical coordinates

 Resolution in case of hydrogen atome
SCHRÖDINGER EQUATION E: the energy eigen value of the electron
Second-order differential Solution
equation
: the eigen function of the electron

Property of the energy eigenvalue

Solving the Schrödinger equation H(Ψ) = EΨ will give physically acceptable

solutions for the energy eigenvalue. For the hydrogen atom, these energy
eigenvalues ​are given by the relation:

𝟏𝟑, 𝟔 𝟐
𝑬𝒏 = − 𝟐 . 𝒁
𝒏

As in Bohr's theory, energy is quantized, and it only depends on the principal

quantum number n.
Property of the eigenwave function 
The solution of the Schrödinger equation leads to the appearance of three numbers called
quantum numbers that determine the eigenvalues of the energy and wave functions, and they
are: n, l, m.
It denotes the principal shell:
The wave function n,l,m depends on 3 quantum numbers. K, L, M, N,…..

“n”: principal quantum number (n  N*) n0 Subshell,

“l” : secondary quantum number or azimuthal (l N) 0  l  (n1) denotes the general shape
of atomique orbitals (AO)
“m” magnetic quantum number (m  Z)  l  m  +l
Denotes the orientation of
(AO), with respect the three
axes in space.

Example: n = 3  0  l  2 then l = 0, 1, 2 (s, p, d)  we have the subshells: 3s, 3p, 3d.

The magnetic quantum number (azimuthal) determines
the total number of orbitals in a subshell as well as their
orientation. It is represented by the symbol m. It is also
called a quantum box.
 Example of quantum numbers combinaision of the levels or shells : 1 and 2

The 2s, 2px, 2py, and 2pz atomic orbitals are degenerate, meaning they are at the same
energy level (or they have the same energy) in the hydrogen case.
 Introduction of the spin quantum number

To completely describe an electron in an atom, a fourth quantum number (s or

ms) must be assigned to it.

The existence of this quantum number is demonstrated by the emission spectrum

of alkali metals (atoms with a single peripheral electron) and then confirmed by
the Stern-Gerlach experiment.
Emission spectrum of sodium (in the visible)

The electron rotates around its axis

(spins), making it similar to a tiny
magnet. This results in a spin quantum
number, which can take only two values,
+1/2(↑)up arrow or -1/2(↓) down arrow.
 Energy diagram of the hydrogen atom

Degenerate orbitals
=
Orbitals with the
same energy level

In general, for a given n shell (n  4), there will be n subshells, n2 orbitals

and a maximum of 2 n2 electrons.
Application exercice: Complete this table

True or If true,
Orbitals false indicate the
orbital
0,0,0
1,1,1
1,0,0
1,1,0
2,1,0
3,2,-2
4,3,3
VII. Representation of Atomic Orbitals (AO): case of hydrogen (Z = 1)

Knowing that the wave function

is written as the product of two
fuctions: radial and angular

1. Function expressions Rn,l (r) and Yl,m (, ) of orbitals 1s, 2s and 2p:

Z denotes the atomic number of the hydrogenoid and a0 = 0,53 Å

2. Study of the radial parts of the “s” and “p” orbitals

a. 1s orbital (n = 1, l = 0) : the radial part of this orbital is:

𝟐 −𝒂𝒓
𝑹(𝒓)𝟏𝒔 = 𝒆 𝟎
𝒂𝟑𝟎
2𝑟
2 4𝑟 2 − 𝑎
We write the radial probability as: 𝑑𝑃 𝑟 = 𝑅(𝑟) 𝑟 2 𝑑𝑟 = 3 𝑒 0 𝑑𝑟
𝑎0

2𝑟
𝑑𝑃(𝑟) 4𝑟 2 − 𝑎
The probability density is then written: = 3 𝑒 0
𝑑𝑟 𝑎0

The probability is zero for r = 0 and

r = + .
It maximized at r = a0.
b. 2s orbital (n = 2, l = 0) : the radial part of this orbital is:
𝟏 𝒓 𝒓
−
𝑹(𝒓)𝟐𝒔 = 𝟏− 𝒆 𝟐𝒂𝟎
𝟐𝒂𝟎
𝟐𝒂𝟑𝟎
2 𝑟
2 𝑟2 𝒓 −
We write the radial probability as: 𝑑𝑃 𝑟 = 𝑅(𝑟) 𝑟 2 𝑑𝑟 = 𝟏− 𝑒 𝑎0 𝑑𝑟
2𝑎03 𝟐𝒂𝟎

2 𝑟
𝑑𝑃(𝑟) 𝑟2 𝒓 −𝑎
The probability density is then written: = 𝟏 − 𝟐𝒂 𝑒 0
𝑑𝑟 2𝑎03 𝟎

The probability of finding an electron

is maximized at two values of the
distance r, 0,77 a0 and 5,23 a0.

There is 1 nodal plane for r = 2 a0, in

wich, the probability of finding an
electron is zero.

This plane is called a "node". In

general, for an orbital (ns), there are
(n-1) nodal surfaces or node.
c. 2p orbitals (n = 2, l = 1) : The radial part of these three orbitals is:
𝟏 𝒓
−
𝑹(𝒓)𝟐𝒑 = 𝒆 𝟐𝒂 𝟎

𝟐 𝟔 𝒂𝟑𝟎
𝑟
2 𝑟2 −
We write the radial probability as: 𝑑𝑃(𝑟)2𝑝 = 𝑅(𝑟) 𝑟 2 𝑑𝑟 = 𝑒 𝑎0 𝑑𝑟
24 𝑎03

𝑟
𝑑𝑃(𝑟) 𝑟2 −
The probability density is then written: = 3 𝑒 𝑎0
𝑑𝑟 2𝑝 24 𝑎0

The probability is zero for r = 0 and r = + 

and it maximized at r = 4a0.
3. Shape of the “s” and “p” orbitals

a. (ns) orbitals (l = 0, m = 0):

𝟏
. independent of the angle θ and φ.
The angular wave function is equal to 𝟐
Hence, the probability of finding the electron is independent of the direction
from the nucleus. So, the shape of the s orbital is spherical.
b. (np) orbitals: (l = 1 m = -1, 0, +1):

The three different m values indicates that there are three different
orientations possible for p orbitals. These orbitals are designated as px , py
and pz . The shape of p orbitals are dumb bell shape.

Angular wave function

 THE POLYELECTRONIC ATOM IN WAVE MECHANICS

I. Introduction :
The resolution of the Schrödinger equation is impossible in the case of poly-
electronic atoms or ions; one must take into account the nucleus-electron
attraction forces and the electron-electron repulsion forces.

In this case, it is necessary to make approximations to determine approximate

wave functions and the energies of the system. One of the approximations studied
in this course is the Slater approximation.
 SLATER’S APPROXIMATIONS OR RULES
In quantum physics and computational chemistry, Slater's
rules are a set of empirical rules that are used to evaluate
the effective nuclear charge.

In a multi-electron atom, the effective charge perceived by

each electron is Z* = Z – , where Z is the actual nuclear
charge and  represents the screening effect produced by
the electrons.

These rules were proposed in 1930 by the American

physicist John Clarke Slater.
American atomic and
molecular physicist
1900-1976
1. ELECTRON ORBITAL ENERGY IN THE SLATER APPROXIMATION:

The energy of atomic orbitals in a polyelectronic atom depends on the two

quantum numbers n and l.

The energy of the atom = the sum of the orbital energies of all its electrons

Ei = En,l : electron orbital energy

Xi : number of electrons occupying each energy orbital Ei

 2. Calculation of the effective charge : Z* =Z−σ

Example: Calculate the energy of the carbon atom using the Slater approximation.

We first determine the effective charge of one electron from each shell of the 6C electron.
Configuration of the atom: (1s2 ) (2s2 2p2).
The two 1s electrons each feel the screening effect of the
other electron. σ1S = 0.3  Z1s* = 6 - 0.3= 5.7

And the four external electrons (2s 2p) each feel the screening
effect of:
• the other three electrons in the same shell
• the two electrons in the 1s shell with: σ2S2P = 2.75 
Z2s2p* = 6-2.75 = 3.25

3. Calculation of the total energy of the carbon atom:

II. Rules for Establishing Electron Configuration:
The electronic configuration of an atom is the distribution of Z electrons of the
atom in a ground state on the atomic orbitals. This filling of the atomic orbitals is
carried out using the following general rules.
1. Principle of stability: Klechkowski's rule:
Electrons occupy the lowest energy levels within the limits of available places.
Electrons start by saturating the lowest energy levels, in the order:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s....
This is the Klechkovski rule, also known as the (n + l) rule.
2. Pauli Exclusion Principle.
Two electrons in the same atom cannot have identical four quantum numbers.

Note:
A quantum box can contain a maximum of 2 electrons with opposite spins.
An empty orbital represents an electron deficiency.

3. Hund's Rule:
In the ground state, when electrons are placed in a multiple subshell (p, d, f):
They occupy the maximum number of orbitals of the same energy. Unpaired
electrons have parallel spins (same spin value).
Exceptions to the Klechkowski rule : Chromium group (Z = 24) – Copper groupe (Z = 29)

The Klechkowski rule states that electrons fill orbitals in order of increasing n + l. However,
there are some exceptions to this rule, particularly for transition metals. These elements
have more stable configurations with a half-filled (d5) or fully filled (d10) d subshell.

For chromium, the configuration is [Ar] 4s² 3d4, deviating from the expected
[Ar] 4s¹ 3d5 configuration. This difference is often attributed to the improved
stability achieved through a half-filled 3d subshell. Similarly, copper has an
exception with the [Ar]4s¹ 3d10 configuration instead of [Ar]4s² 3d9, because the
full 3d10 configuration is considered more stable.
 THE SIMPLIFIED ELECTRONIC CONFIGURATIONS
The simplified or abbreviated electronic configurations, also known as noble gas
notation, use the electron configuration of a noble gas to represent the electron
distribution of an element, according to:
NOBLE GAS CONFIGURATION + VALENCE SHELL
We write: [NG] ns2 (n-2)f14 (n-1)d10 np6

For example, the electron configuration of sodium (Z = 11) is: 11Na: 1s2 2s2 3s1
the simplified one is: 11Na[Ne]3s1

Therefore, the outermost electron shell of sodium is 3s1

(only one valence electron).
 ELECTRON CONFIGURATION OF ANIONS:
Anions are formed when the atom gains as many electrons as necessary
to attain the electron configuration of the next noble gas in the periodic
table.
 IN THE CASE OF POSITIVELY IONS (CATIONS):
To write the electronic structure of a positively ionized species:
- General case: The outermost electrons (those corresponding to the largest n) are
removed first.
Example: The electronic configuration of a neutral carbon atom is 1s2 2s2 2p2.
The electronic configuration of a positively charged carbon ion (6C+) is 1s2 2s2 2p1.

- In the case of transition metals: The electrons are removed first from the ns
(highest principal quantum number) orbital and then from the (n-1) d orbitals.
Examples:
 THE VALENCE AND THE CORE SHELLS

The valence shell is the outermost shell of an atom. It is the shell that is furthest
from the nucleus. The core shell is the inner shell of an atom. It is the shell that
is closest to the nucleus.

Example:
 VALENCE AND CORE ELECTRONS
There are two types of electrons in an atom as valence electrons and core
electrons. Valence electrons reside at the outermost shells while core electrons are
in the inner shells. The key difference between valence and core electrons is that
valence electrons participate in the chemical bond formation while core electrons
do not.
Other examples
Four elements were identified between 2004 and 2010: Nihonium 113 (Nh),
discovered by the Japanese physicist Kosuke Morita. It is named "nihonium" in
reference to the word "Nihon," meaning Japan.

Discovered by a collaboration of two research centers in Tennessee and Moscow,

elements 115 and 117 are named "moscovium" and "tennessine" respectively.

Element 118, "oganesson" is named after the physicist Yuri Oganessian, a Russian
scientist.

These superheavy elements officially became part of the periodic table in 2015, and
the International Union of Pure and Applied Chemistry (IUPAC) revealed their
names in 2016.