Chapter I: The Atom, Electronic Structure

1) Atomic scale: atomic nucleus and atom

1.1) The nucleus of atoms. 1.2) The atom. 1.3) Atomic mass, mole.

2) Quantization of energy in bound systems.

3) Bohr's atomic model.

4) De Broglie wave.

5) The principle of quantum mechanics.

6) Wave functions, orbitals.

7) Electronic states and energy level diagrams of electronic states.

7.1) Hydrogen atom and hydrogen-like atoms. 7.2) Polyelectronic atoms. 7.3) Distribution of
electrons in states.

● 7.3.1) Electron spin.

● 7.3.2) Pauli exclusion principle.
● 7.3.3) Stability principle.
● 7.3.4) Hund's rule.
● 7.3.5) Excited states.

The goal: To understand the electronic environment of an atom in order to explain its bonding
possibilities. This will also lead to understanding charge distribution in a molecule and its
physicochemical properties.

1) Atomic scale: atomic nucleus and atom

The distance scales in the universe:

10^26 m - The edge of the universe

10^21 m - 100,000 light years, size of galaxies
10^16 m - 1 light year (it is 4 light years to the closest star)
10^11 m - 100 million kilometers (diameter of Mercury’s orbit around the sun)
10^6 m - 1,000 kilometers (Toulouse to Dunkirk: 965 km)
10^0 m - Immediate surroundings
10^-4 m - 1/10 mm, 100 microns, size of bacteria (optical microscope)
10^-9 m - 1 nanometer, 10 Ångström, size of small molecules
10^-14 m - 10 femtometers, size of large atomic nuclei
10^-19 m - Limit of knowledge by the end of the 20th century (quarks and leptons)

Classical mechanics laws do not apply to very small particles.

1.1) The nucleus of atoms

The nucleus = protons + neutrons, the proton is electrically charged (>0), and the neutron is
uncharged.
Nucleons: refers to both protons and neutrons.

1.2) The atom

Atom = nucleus + electron(s)

The electrostatic interaction between the nucleus and the electrons ensures the atom's stability.
It is always characterized by its atomic number, which is the number of protons. If neutral, the
number of electrons is also Z; if ionized, the atom has some additional or missing charges
(anions or cations).
The chemical behavior of an element is linked to this Z value and the exact state of its electrons
(ionization, bonding).
Mass of the proton/mass of the electron = 1831; the atom’s mass is concentrated primarily in its
nucleus.
Atomic radius/nuclear radius = 10^4 to 10^15 (spherical model).

1.3) Atomic mass, mole

A mole of an elementary entity (symbol mol) is the quantity of that entity equal to Avogadro's
constant (NA), which is fixed at exactly 6.02214076 × 10^23 (mol^-1).

The carbon-12 isotope, the most abundant natural form of carbon, is used as the reference for
atomic masses.

Conversion factor: 1 u = 1.66054 × 10^-27 kg.

2) Quantization of Energy in Bound Systems

Hydrogen atom = 1 proton + 1 electron.

Convention: The energy of the proton-electron system is zero when the electron at rest is free
from any interaction with the nucleus (i.e., at an infinite distance from each other). Hence, the
system’s energy is always less than or equal to zero. The most stable state is the one with the
lowest energy.

Emission spectrum of the hydrogen atom:

Quantum theory suggests that energy exchanges between matter and radiation can only occur
in multiples of a minimum energy quantity called a quantum.
1 quantum = hνh\nuhν (joules)

This implies a dual nature: corpuscular (photon flux) and wave-like (electromagnetic radiation).

3) Bohr’s Atomic Model (1913)

Bohr’s model suggests that electrons in an atom can only occupy certain discrete energy levels.
Each energy corresponds to a stable circular orbit around the nucleus, where the electron does
not lose energy. The electron's energy changes discontinuously as it jumps from one level to
another during absorption or emission of energy.

In the absence of external excitation, an electron remains at the lowest possible energy level.
Transitions between energy levels occur in discrete jumps (known as transitions).

4) De Broglie Wave (1923)

De Broglie proposed that every particle (like photons and electrons) has an associated wave
function that depends on spatial coordinates. For any particle with momentum ppp, the
associated wavelength λ is given by:

λ=p/h

The wave nature of electrons was experimentally confirmed by Davisson and Germer in 1927.
Their experiment involved the reflection of low-energy electrons by a nickel crystal, showing
electron diffraction similar to X-ray diffraction by crystals.

In 1954, Möllenstedt demonstrated electron interference, further supporting the wave-like

behavior of electrons.

5) The Principle of Quantum Mechanics

Elementary particles behave differently from classical physics representations. Quantum

mechanics, a new theory, provides a correct description of these particles. In quantum
mechanics, the state of a particle is described by a wave function Ψ(x,y,z,t)\Psi(x, y, z,
t)Ψ(x,y,z,t), which is a solution to a differential equation incorporating the constraints on the
particle. This equation for non-relativistic particles is known as the Schrödinger equation.

6) Wave Functions and Orbitals

The wave function associated with a particle does not have direct physical meaning, but its
square gives the probability of finding the particle in a given region. To represent important
features of the wave function (such as symmetry, sign, and nodal planes), isodensity surfaces
are used. These surfaces define a volume in which the particle's presence is highly probable
(0.95 probability).

A stationary, time-independent wave function for a single electron is called an orbital. In

practice, the term "orbital" is also used for diagrams representing isodensity surfaces.

7) Electronic States and Energy Level Diagrams

7.1) Hydrogen atom and hydrogen-like atoms

A hydrogen-like atom is any atom that has lost all its electrons except one. For such systems,
solving the Schrödinger equation analytically is possible. For the hydrogen atom, the energy
level of a state depends solely on the value of the principal quantum number nnn. Multiple
states (represented by different Ψ wave functions) can exist at the same energy level, which is
known as degeneracy.

7.2) Polyelectronic atoms

In atoms with multiple electrons, electron-electron interactions occur. For example, the 1s
electron in a uranium atom is in the same state as the 1s electron in a hydrogen atom, but their
energy levels differ due to the presence of more protons and electrons in uranium. The energy
of an electron in a polyelectronic atom is influenced by the other electrons, and the effective
nuclear charge is reduced by the screening effect of these other electrons.

7.3) Distribution of Electrons in States

● 7.3.1) Electron Spin

The electron has an intrinsic angular momentum or "spin," which can take two possible
orientations in a magnetic field. This property is described by the quantum number s=12s = \
frac{1}{2}s=21, and the electron’s spin can either be +1/2 or -1/2.

● 7.3.2) Pauli Exclusion Principle

No two electrons in the same atom can have identical sets of quantum numbers (i.e., they
cannot occupy the same quantum state simultaneously).

● 7.3.3) Stability Principle

In an atom, electron configurations follow the rule of filling the lowest available energy levels first
(ground state configuration) while respecting the Pauli exclusion principle.

● 7.3.4) Hund's Rule

For orbitals of the same energy level (degenerate orbitals), the most stable configuration is the
one with the maximum number of unpaired electrons with parallel spins.

● 7.3.5) Excited States

An atom is in an excited state when one or more of its electrons occupy higher energy levels
than the ground state. For example, the carbon atom can have an excited state configuration
like 1s² 2s¹ 2p³ instead of its ground state 1s² 2s² 2p².

Chapter II: The Periodic Table

1) The principle of the periodic table

For a standard reading from left to right and top to bottom, the elements are arranged in
increasing order of their atomic numbers (Z). Several presentations meet these criteria, with the
18-column format being the most used.

The periodic table distinguishes between s, p, d, and f blocks. The lanthanides and actinides,
corresponding to the filling of the 4f and 5f subshells, are represented on two separate lines at
the bottom of the table.

● s block: ns1 or ns2

 ● p block: npx (x = 1 to 6)
● d block: ndx (x = 1 to 10)
● f block: nfx (x = 1 to 14)

The columns (or element families or groups) are assigned Roman numerals representing the
number of valence electrons. The distinction between subgroups A and B comes from the
nature of the valence electrons. For subgroup A (s and p blocks), the valence electrons are
described by s and/or p orbitals, while for subgroup B (d block), the valence electrons are
described by s and/or d orbitals. Elements in the same column have the same number of
valence electrons, conferring similar physicochemical properties (hence the term "element
family"). Family VIIIB consists of three adjacent columns because the elements show analogies
both vertically and horizontally; these are called triads.

Columns are often numbered from Group 1 to Group 18.

The periods (horizontal rows) represent:

● Period 1: ends with 1s

● Period 2: ends with 2s 2p
● Period 3: ends with 3s 3p
● Period 4: ends with 4s 3d 4p
● Period 5: ends with 5s 4d 5p
● Period 6: ends with 6s 4f 5d 6p
● Period 7: ends with 7s 5f 6d 7p (incomplete)

2) Element Families

● Family IA: Includes hydrogen and alkali metals (Li, Na, K, Rb, Cs). These elements are
always monovalent and easily lose one electron. The resulting ions (Li+, Na+, etc.) are
particularly stable and have the electronic structure of the nearest noble gas.
● Family IIA: Includes beryllium (Be), magnesium (Mg), and alkaline earth metals (Ca, Sr,
Ba). These metallic elements are typically divalent and easily lose two electrons, forming
stable ions with the electronic structure of the preceding noble gas.
● Family IIIA: The first element, boron (B), is a non-metal. The following elements (Al, Ga,
In, Tl) are trivalent metals whose metallic character is significantly reduced compared to
Group IIA.
● Family IVA: The first three elements (C, Si, Ge) are non-metals. The two heavier
elements (Sn, Pb) are metallic. These elements are generally tetravalent.
● Family VA: (N, P, As, Sb, Bi) shows decreasing metallic character, except for the
heaviest elements. Valences of 3 and 5 are most common.
● Family VIA: (O, S, Se, Te) are non-metals. Valence 2 is most frequent, but valences of
4 and 6 are also possible (except for oxygen).
● Family VIIA: The halogens (F, Cl, Br, I) are characterized by their high electron affinity.
The resulting anions (F-, Cl-, etc.) are very stable and have the electronic structure of
the nearest noble gas.
● Family 0: The noble gases (He, Ne, Ar, Kr, Xe) are characterized by their chemical
inertness.
3) Evolution of Chemical Properties

3.1) Metals and Non-Metals

● Metals tend to lose electrons easily and form cations, whereas non-metals tend to gain
electrons and form anions.
● Metals generally have lower ionization energies compared to non-metals.

3.2) Ionization Energy

The energy required to remove an electron from an atom or ion. Ionization energies generally
increase across a period from left to right and decrease down a group.

3.3) Electron Affinities

The energy change when an electron is added to a neutral atom. Elements with high electron
affinities tend to form stable anions.

3.4) Electronegativity

The tendency of an atom to attract electrons in a chemical bond. It increases across a period
and decreases down a group.

3.5) Polarization, Dipole Moment

Polarization occurs when there is an uneven distribution of electron density in a molecule,

creating a dipole moment, which can affect the physical properties like boiling point and
solubility.

Chapter III: Molecular Structures

1) Lewis Formula

1.1) The principle.

1.2) The octet rule.
1.3) Examples.
1.4) Limitations of the Lewis method.

2) Predicting geometry: Valence shell electron pair repulsion (VSEPR) method (Gillespie's
rules).

3) Covalent Bond: C.L.O.A. Method

3.1) Theoretical results for the molecular ion H₂⁺.

3.2) The principle of the C.L.O.A. method.
3.3) Homonuclear diatomic molecules (type A₂).
3.3.1) Experimental data.
3.3.2) Construction of molecular orbital diagrams.
3.4) Heteronuclear diatomic molecules (type AB).
4) Conclusion

1) Lewis Formula

1.1) The principle

In 1916, Lewis proposed a simple model for the covalent bond: molecules form by assembling
atoms that share their valence electrons. The core electrons are held too tightly by the nucleus
to participate in bonding. Therefore, electron pairs are created, responsible for the stability of
polyatomic entities, with each pair constituting a covalent bond. This bond can form in two ways:
either each atom contributes one electron, or one atom donates both electrons to a deficient
atom (dative bond).

Some valence electrons do not participate in bonding and remain as lone pairs. A single bond
shares one pair, a double bond shares two pairs, a triple bond shares three, and in rare cases
(e.g., rhenium compounds), a quadruple bond is formed.

1.2) The octet rule

Lewis suggested the octet rule for atoms in the second and third periods: maximum stability is
achieved when an atom is surrounded by four electron pairs (an octet, akin to noble gases,
which rarely form compounds).

2) Predicting geometry: Valence shell electron pair repulsion (VSEPR) method

This method predicts molecular geometry based on the idea that electron pairs around a central
atom will arrange themselves to minimize repulsion. Gillespie's rules are applied to determine
the 3D arrangement of atoms in a molecule.

3) Covalent Bond: C.L.O.A. Method

The C.L.O.A. (Combinaison Linéaire des Orbitales Atomiques) method describes molecular
bonding using linear combinations of atomic orbitals. This theory is used to explain bonding in
both homonuclear and heteronuclear diatomic molecules.

3.1) H₂⁺ molecular ion

For the simplest case, H₂⁺, bonding is described by the overlap of atomic orbitals.

3.2) Principle of C.L.O.A.

The method combines atomic orbitals to form molecular orbitals. These orbitals can either be
bonding (lower energy) or anti-bonding (higher energy). Electrons occupy the lowest available
energy levels, respecting the Pauli exclusion principle.

3.3) Homonuclear diatomic molecules (A₂ type)

● 3.3.1) Experimental data: The bond lengths, dissociation energies, and force constants
of homonuclear diatomic molecules (H₂, O₂, N₂, F₂, etc.) are measured.
● 3.3.2) Molecular orbital diagram construction: Molecular orbitals are arranged in
increasing energy levels, based on symmetry and overlap of atomic orbitals.
3.4) Heteronuclear diatomic molecules (AB type)
In molecules like HF, differences in electronegativity create bonding and anti-bonding molecular
orbitals, with electrons shared unevenly between atoms.

Chapter IV: Molecular Interactions

1) Boiling Point

In the gaseous state, molecules are far apart, particularly when the pressure is low. They are in
constant motion and can travel long distances (compared to their size) before colliding with
another molecule. This is a non-condensed, disordered state.

In the liquid state, molecules are in contact with each other. Their movements are limited, but
molecular agitation exists, and their relative positions are constantly changing. This is a
condensed but disordered state.

Raising the temperature increases the kinetic energy of the molecules, explaining the transition
to a more disordered state (liquid to gas). However, this does not explain the abrupt appearance
of the gaseous state (boiling) at a certain temperature. There are intermolecular attractive forces
that ensure liquid cohesion. At the boiling point, molecules have just enough kinetic energy to
overcome these cohesive forces and escape from the liquid to form gas. Thus, the stronger the
cohesive forces, the greater the kinetic energy required to break free, and the higher the boiling
point.

Similarly, all else being equal, the greater the molar mass, the more energy is required for
molecules to leave the liquid phase.

2) Polarity

2.1) Permanent Dipole Moment

A permanent dipole occurs when there is an imbalance in the distribution of electrical charges
within a molecule, resulting in one side being more positively or negatively charged.

2.2) Polarizability, Induced Dipole Moment

Polarizability refers to a molecule's ability to distort its electron cloud under an external electric
field (such as the presence of a nearby ion or dipole), creating an induced dipole moment.

3) Van der Waals Interactions

Van der Waals forces are electrostatic attractions between molecules due to localized positive
and negative charges. These forces manifest in three forms:

● Between two permanent dipoles (Keesom forces),

● Between a permanent dipole and an induced dipole (Debye forces),
● Between two instantaneous dipoles (London dispersion forces).
London dispersion forces occur even between nonpolar molecules, as every molecule exhibits
an instantaneous dipole at any given time due to electron movement.

4) Hydrogen Bonding

When a hydrogen atom is bonded to a highly electronegative atom (O, N, F), it carries a
significant partial positive charge due to the strong polarization of the bond. This positive charge
attracts the partial negative charge of neighboring electronegative atoms, forming a hydrogen
bond.

Hydrogen bonds are about ten times stronger than other dipole-dipole interactions but ten times
weaker than covalent bonds. A hydrogen atom involved in a hydrogen bond remains more
strongly attached to its original molecule than to the molecule with which it forms the hydrogen
bond.