Study unit 2: Principles of Quantum Chemistry and Periodicity / Electronic

Structure and Periodic Properties of Elements

• In order to study the electronic structure of the atoms (elements) we
need to use the concept of quantum numbers.
• An atom consists of a small, positively charged nucleus (protons &
neutrons) around which electrons revolve in definite circular paths
called orbits.
• These orbits are associated with definite energies called energy shells
(levels), numbered 1, 2, 3, 4, … from the nucleus outward.
• Quantum numbers are used to describe an electron in an atom, in
which there is different clouds of probability or orbitals where
electrons can occur around an atom, and these orbital are: s orbital,
the second a p orbital, then a d orbital, an f orbital and so on.
 Understanding Quantum Theory of Electrons in Atoms
• To understand the electronic structure of any atom (element), one
needs to understand the electron orbitals (location of electrons in
atoms), their different energies, and other properties.

• The energy levels are labeled with an n value, where n = 1, 2, 3,. …,

and This number, n, is referred to as the principal quantum number
(also called shell number / level ).

• The principal quantum number defines the location of the energy

level / shell.
• All orbitals that have the same value of n are said to be in the same
shell. The shell with n = 1 is called the first shell, the shell with n = 2 is
the second shell, and so forth.
• The principal quantum number is related to the size of the electron
wave (i.e., how far the wave effectively extends from the nucleus).
The higher the value of n, the larger is the electron’s average distance
from the nucleus.

• This quantum number is also related to the energy of the orbital. As

n increases, the energies of the orbitals also increase.

• So the further away the electron is from the nucleus, the greater the
energy it has.
The Secondary Quantum Number, ℓ / Azimuthal quantum number or
angular quantum number (ℓ)

• This secondary quantum number, divides the shells into smaller

groups of orbitals called subshells.

• The azimuthal quantum number (ℓ) is related to shape. It answers

questions such as: What shape is an s orbital? What shape is a p
orbital?

• It is an integer that may take the values, ℓ = 0, 1, 2, …, n – 1. This

means that an orbital with n = 1 can have only one value of ℓ = 0,
whereas n = 2 permits ℓ = 0 and ℓ = 1, and so on.
• Thus, when n = 1, (n -1) = 0, so the only value of ℓ that’s allowed is
zero. This means that when n = 1, there is only one subshell (the shell
and subshell are really identical).

• When n = 2, ℓ can have a value of 0 or 1. (The maximum value of ℓ = n

- 1 = 2 - 1 = 1.) This means that when n = 2, there are two subshells.
One has n = 2 and ℓ = 0, and the other has n = 2 and ℓ = 1.
 Subshells could be identified by the numerical value of ℓ. However,
to avoid confusing numerical values of n with those of ℓ, a letter
code is normally used to specify the value of ℓ.

To designate a particular subshell, we write the value of its principal quantum number followed by the letter code
for the subshell.

For example, the subshell with n = 2 and ℓ = 1 is the 2p subshell.

i,e, if n = 2, then the possible subshells are (ℓ = 0, and 1). So in this example, they chose subshell ℓ = 1, so since
n = 2 (principal quantum number), then we have a 2p subshell / orbital.

- Suppose they chose subshell ℓ = 0, then we will have a 2s subshell / orbital

 Other examples,
• The subshell with n = 4 and ℓ = 0 is the 4s subshell.

• i,e, if n = 4, then the possible subshells are (ℓ = 0, 1, 2 and 3). So in

this example, they chose subshell ℓ = 0, so since n = 4 (principal
quantum number), then we have a 4s subshell / orbital.

Notice that because of the relationship between n and ℓ, every shell has an s subshell (1s, 2s, 3s,
etc.).

All the shells except the first have a p subshell (2p, 3p, 4p, etc.).

All but the first and second shells have a d subshell (3d, 4d, etc.); and so forth.
 The Magnetic Quantum Number, mℓ
• The third quantum number, mℓ, is known as the magnetic quantum
number. It divides the subshells into individual orbitals, and its
values are related to the way the individual orbitals are oriented
relative to each other in space.

• Allowed values for mℓ can only be integral values from -ℓ to +ℓ,

including 0.

• When ℓ = 0, mℓ can have only the value 0 because +0 and -0 are the
same.
• Therefore, An s subshell (of which ℓ = 0), then, has just a single
orbital, with mℓ = 0.
• A p subshell therefore has three orbitals: one with ℓ = 1 and mℓ = -1,
another with ℓ = 1 and mℓ = 0, and a third with ℓ = 1 and mℓ = +1.
• Similarly, we find that a d subshell has five orbitals.

• This is because d subshell (of which ℓ = 2), can have mℓ integral

values from -ℓ to +ℓ (-2, -1, 0, 1 and 2), i.e five orbitals.

• an f subshell has seven orbitals. This is because f subshell (of which ℓ

= 3), can have mℓ integral values from -ℓ to +ℓ (-3, -2, -1, 0, 1 ,2 and
3), i.e seven orbitals.
• Remember, each orbital can take 2 electrons, so a p orbital with 3
orientations actually has 3 p orbitals available and thus can contain 6
electrons (2 in each orbital).

• An s orbital with only 1 orientation actually has 1 s orbital available

and thus can contain 2 electrons.

• a d orbital with 5 orientations actually has 5 p orbitals available and

thus can contain 10 electrons (2 in each orbital).
The relationships among all three quantum numbers studied so far
are summarized in Table below.
 Spin quantum number (ms)
• The final property, which actually describes the electrons and not the
orbitals, is called spin.

• The orientation of spin of an electron is indicated by its spin quantum

number ms.

• Allowed values for ms can only be two values, namely +½ (clockwise

spin) or -½ (anticlockwise spin).
 Pauli Exclusion Principle

• The Pauli exclusion principle states that no two electrons in the same atom
can have identical values for all four of their quantum numbers.

• Suppose two electrons were to occupy the 1s orbital of an atom. Each

electron would have n = 1, ℓ = 0, and mℓ = 0.

• Since these three quantum numbers are the same for both electrons, the
exclusion principle requires that their fourth quantum numbers (their spin
quantum numbers, ) be different; one electron must have ms = + ½ and the
other, ms = − ½. In other words, they must be paired
• when two electrons occupy the same orbital they must have different
values of ms.

• Atoms with more electrons that spin in one direction than in the other are
said to contain unpaired electrons.

• For these atoms, the magnetic effects do not cancel and the atoms
themselves become tiny magnets that can be attracted to an external
magnetic field.

• This weak attraction of a substance containing unpaired electrons to a

magnet is called paramagnetism.

• Substances in which all the electrons are paired are not attracted to a
magnet and are said to be diamagnetic.
• No more than two electrons can occupy the 1s orbital of the atom
simultaneously because there are only two possible values of ms.

• Thus, the Pauli exclusion principle is really telling us that the

maximum number of electrons in any orbital is two, and that when
two electrons are in the same orbital, they must have opposite spins.
• Therefore, any atomic orbital can be populated by only zero, one, or
two electrons.
• The limit of two electrons per orbital also limits the maximum
electron populations of the shells and subshells. For the subshells we
have:
Calculate the maximum number of electrons that can occupy a
shell with (a) n = 2, (b) n = 5,
 Electronic Structure of Atoms (Electron
Configurations)

• The distribution of electrons among the orbitals of an atom is called

the atom’s electronic structure or electron configuration.

• This is very useful information about an element because the

arrangement of electrons in the outer parts of an atom, which is
determined by its electron configuration, controls the chemical
properties of the element.
To arrive at the electron configuration of an atom of another
element, we imagine that we begin with a hydrogen atom and then
add one proton after another (plus whatever neutrons are also
needed) until we obtain the nucleus of the atom of interest.

As we proceed, we also add electrons, one at a time to the lowest

available orbital, until we have added enough electrons to give the
neutral atom of the element.

This imaginary process for obtaining the electronic structure of an

atom is known as the aufbau principle.
 Orbital Energies and Atomic Structure
• The energy of atomic orbitals increases as the principal quantum
number, n, increases.

• The energy of the orbitals increases within a shell in the order s < p <
d < f.
• The 1s orbital at the bottom of the diagram is the orbital with
electrons of lowest energy.
• The energy increases as we move up to the 2s and then 2p, 3s, and 3p
orbitals, showing that the increasing n value has more influence on
energy than the increasing l value for small atoms.
• However, for larger atoms, the 3d orbital is higher in energy than the
4s orbital.
• For small orbitals (1s through 3p), the increase in energy due to n is
more significant than the increase due to ℓ;

• however, for larger orbitals the two trends are comparable and
cannot be simply predicted.

• In order to describe an electron configuration, we use a symbol that

contains three pieces of information: for example, hydrogen element
(H) contains only 1 election
• 1. The number of the principal quantum shell, n,

• 2. The letter that designates the orbital type (the subshell, ℓ), and

• 3. A superscript number that designates the number of electrons in

that particular subshell.

• the notation 2p4 (read "two–p–four") indicates four electrons in a p

subshell (ℓ = 1) with a principal quantum number (n) of 2. The
notation 3d8 (read "three–d–eight") indicates eight electrons in the d
subshell (i.e., ℓ = 2) of the principal shell for which n = 3.
 The Aufbau principle
• The Aufbau principle states that the electrons in an atom are arranged so that they
occupy orbitals in order of their increasing energy.

• According to this principle the orbital with the lowest energy is filled first.

• Once an orbital has the maximum number of electrons it can hold, it is considered filled.

• Remaining electrons must then be placed into the orbital with the next highest energy.

• Hund’s rule: Hund’s rule states that when degenerate orbitals (orbitals of the same
energy) are available, electrons first occupy these orbitals singly with parallel spins
• before pairing.

• By convention, the ms = +1/2 value is usually filled first

Electron Configurations & Orbital diagrams
valence electrons & core electrons / Valence Shell Electron Configurations /
NOBLE GAS CORE NOTATION
• The electrons occupying the outermost shell orbital(s) (highest value
of n) are called valence electrons, and those occupying the inner shell
orbitals are called core electrons.

• Since the core electron shells correspond to noble gas electron

configurations, we can abbreviate electron configurations by writing
the noble gas that matches the core electron configuration, along
with the valence electrons in a condensed format.
Draw the energy orbital diagram of the phosphorus atom above. Is the
atom paramagnetic or diamagnetic?

And the atom is paramagnetic

 Electron Configurations of Ions
• An ion is a charged species formed through either the loss or the gain
of an electron or electrons.

• A neutral atom (an atom with an equal number of protons and

electrons) may lose an electron or electrons to become a positively
charged ion, called a cation.

• A neutral atom can also gain an electron or electrons to become a

negatively charged ion called an anion.
The only electrons that are normally important in controlling chemical properties are the ones in the outer shell.

This outer shell is known as the valence shell, and it is always the occupied shell with the
largest value of n. The electrons in the valence shell are called valence electrons.
 Trends in atomic size, ionization energy, and electron affinity of the
elements

• As we go across a period from left to right, we add a proton to the

nucleus and an electron to the valence shell with each successive
element.

• As we go down the elements in a group, the number of electrons in

the valence shell remains constant, but the principal quantum
number increases by one each time.
• The effective nuclear charge felt by the outer electrons of the atoms
in a group on the periodic table is nearly constant.

• However, the principal quantum number n increases and the orbitals

become larger from top to bottom within a group. As a result the
atomic radius and size increase down the group.

• The principal quantum number n is the same across the period.

However, the effective nuclear charge increases.

• This causes the negatively charged electrons to be pulled inwards,

thus decreasing the size of the atom from left to right across a
period.
 Trends in atomic size, ionization energy, and electron affinity of the
elements
• Atomic radius decreases from left to right in a period and increases
from top to bottom in a group.

• The overall size of ions (ionic radius) follows the same trend as that of
the neutral atoms discussed in the paragraphs above.

• Negative ions (anions) are larger than the neutral atom because the
extra electrons cause more electron repulsion, which increases the
volume of the electron cloud.

• In positive ions (cations) there is a decrease in electron repulsion and

the size of the electron cloud is smaller than that of the neutral atom.
• Atoms and ions that have the same electron configuration are said to
be isoelectronic.

• Examples of isoelectronic species are N3–, O2–, F–, Ne, Na+, Mg2+, and
Al3+ (1s22s22p6).

• Another isoelectronic series is P3–, S2–, Cl–, Ar, K+, Ca2+, and Sc3+
([Ne]3s23p6).
 Variation in Ionization Energies
• The first ionization energy (abbreviated IE1) is the energy required to
remove an electron from an isolated, gaseous atom or ion in its
ground state.
• In effect, the ionization energy is a measure of how much work is
required to pull an electron from an atom, so it reflects how tightly
the electron is held by the atom.
• The energy required to remove the second most loosely bound
electron is called the second ionization energy (IE2).
• The energy required to remove the third electron is the third
ionization energy, and so on.
• For larger atoms, the most loosely bound electron is located farther
from the nucleus and so is easier to remove.

• As size (atomic radius) increases, the ionization energy should

decrease, and vise-versa.

• Therefore, ionization energies decrease down a group (since atomic

radius and size increase down the group) and ionization energies
increase across a period (since Atomic radius decreases from left to
right in a period ).
Variation in Ionization Energies
 Electronegativity

• Electronegativity is a measure of the ability of an atom to attract the

shared electrons to itself when bonded to another atom in a
molecule.

• Fluorine (the most electronegative element) is assigned a value of 4.0,

and values range down to caesium and francium, which are the least
electronegative at 0.7.

• Electronegativity increases from left to right across a period, and it

decreases down a group.
 Variation in Electron Affinities
• The electron affinity (EA) is the energy change for the process of
adding an electron to a gaseous atom to form an anion (negative
ion).
• EA as the energy change associated with adding one mole of
• electrons to one mole of gaseous atoms or ions.
• When an electron is added to a gaseous neutral atom, energy is
released (i.e. the reaction is exothermic).

• This energy, known as electron affinity (EA), is given a negative value.

• For nearly all the elements, the addition of one electron to the
neutral atom is exothermic, and the EA is given as a negative value.

• Although there are some irregularities, overall the electron affinities

of the elements become more exothermic going from left to right
across a period and from bottom to top in a group.

• This is because: Electronegativity increases from left to right across

a period, and it decreases down a group.