Quantum theory and the electronic

structure of atoms

• Electronic structure of an atom refers to the

arrangement of electrons in an atom.
• Visible light is a form of Electromagnetic
radiation (radiant energy).
• Radiation carries energy through space
• Electromagnetic radiation is characterized by its
wave nature
 Quantized Energy and Photons
• The wave nature of light could not explain phenomena
such as:
• Blackbody radiation- an emission of light from hot
objects.

• The photoelectric effect- the ejection of electrons from

metal surfaces on which light shines.
• The emission spectra- the emissions of light from
electronically excited gas atoms.
 Emission Spectra of Atoms

• Emission spectra of atoms

does not show a continuous
spectrum as one gets from a
white light source
 But only a line
spectrum of discrete
wavelengths is
observed
 A line spectrum
represents a fingerprint
signature for elements
 Emission Spectra of Atoms

• Bohr’s theory enables us to explain the line

spectrum of the hydrogen atom. He proposed
that the energy of the electron in hydrogen
atom is quantized.
• Bohr model assumed electrons to be particles
moving in circular orbits around the nucleus
and that these orbits have certain defined
energy values.
• - When energy is absorbed by the atom, the
electron jump to the higher energy orbit, and it
is said to be in its excited state..
 Emission Spectra of Atoms

- When an electron moves from a higher energy orbit

to a lower energy orbit, radiation is emitted by the
atom. an electron then occupies the lowest possible
energy level, and it is in its ground state.
. Energy in form of a photon, can only be absorbed
or emitted in quanta given by:
ΔE = h
- When energy is absorbed, ΔE is positive.
- When energy is emitted, ΔE is negative.
• Bohr’s atomic model did not explain several
phenomenon involving electrons, as electrons
are not merely small particles circling the
nucleus but they exhibit wave-like properties
as well.

• The Bohr’s model was further refined by

wave mechanics in which electrons are
considered to be wave-like and their position
is treated in terms of probability distribution.
 Wave-particle duality of electron
• In 1925, Louis de Broglie proposed that since light has
a dual nature with properties of both waves and
particles, then particles of matter such as electrons
should also have a dual nature and exhibit wave
properties as well.
• He proposed that the wavelength () of a particle
depends on its mass m and velocity  (mv = p, which
is the linear momentum).

 =h/ mv = h/p
h is the Planck’s constant.
The Heisenberg Uncertainty Principle
• States that, it's impossible to determine
accurately both the momentum and position of
an electron simultaneously.

• He showed that the more precisely the

momentum of an electron is known, the less
precisely its position is known.
 Quantum Mechanics

• Erwin Schrödinger developed a mathematical

treatment into which both the wave and particle
nature of the electrons could be incorporated.

• This was latter known as quantum mechanics.

 Quantum Mechanics
• The wave function is
designated with a lower case
Greek psi ().

• The square of the wave

function, 2, gives a
probability density map of
where an electron has a
certain statistical likelihood
of being at any given instant
in time.
 Wave-mechanical model
• In the wave –mechanic model, every electron
in an atom is characterized by four parameters
called quantum numbers.
• Solving the wave equation gives a set of wave
functions, or orbitals, and their corresponding
energies.
• Each orbital describes a spatial distribution of
electron density.
• An orbital is described by a set of four
quantum numbers.
- The distribution of electrons in hydrogen and other
atoms can be described by three sets of quantum
numbers derived from the mathematical solution of
the Schrödinger equation.

These are:
1. The principal quantum number (n)
2. The angular momentum quantum number or Azimuthal
quantum number (l)
3. The magnetic quantum number (ml)
4. The spin quantum (ms)
 Principal Quantum Number,

• The principal quantum number, , describes the size

and energy level on which the orbital resides.
 The values of are integers > 0.
i.e.
 as increases, the distance of electron from the
nucleus increases, electron has higher energy and
less tightly bound. = 1 =2 =3

• • •
Angular Momentum (Azimuthal) Quantum Number, ℓ
• This quantum number defines the shape of the
orbital.
• Allowed values of ℓ are integers ranging from 0
up to (n − 1).
• i.e.
• Example: if n = 4
• Then
• We use letter designations to communicate the
different values of ℓ and, therefore, the shapes and
types of orbitals.

Value of ℓ 0 1 2 3 4 …

Name of s p d f g …
orbital
 • A set of orbitals with the same value of n, for
example, 3s, 3p and 3d are called a shell.
 A set of one or more orbitals with the same n and ℓ
values are referred to as subshells.
 Example: n = 2 Shell

ℓ 0 1 3 d subshell
2s 2p
subshell
 These subshells are called:
2 s and 2 p subshells
denotes the denotes the value
value of n of ℓ = 2
 Magnetic Quantum Number, mℓ

• mℓ describes the 3D orientation of the orbital.

• mℓ values are integers ranging from - ℓ to ℓ: The
value of mℓ depends on the value of ℓ.
• mℓ = - ℓ, …, 0, …., + ℓ
• If ℓ = 2, then mℓ = -2, -1, 0, 1, 2
• There are integral values of mℓ. The number of mℓ
values is equal to the number of orbitals in a
subshell.

• ℓ = 2, then it’s a d-subshell.

• Thus a d-subshell has five orbitals (2(2) + 1).

• N.B: Each orbital can hold a maximum of 2

electrons
 Electron/Magnetic Spin Quantum Number, ms

• Electron spin accounts for energy levels in line

spectra. +1 1
𝑚 𝑠= 𝑜𝑟 −
2 2
 Pauli Exclusion Principle
• Pauli Exclusion Principle: No two electrons
in an atom can have the same four quantum
numbers.

• Thus 2 electrons in the same orbital must

have opposite spins!
 Examples
a) How many orbitals are in the shell n = 3?
b) What is the maximum number of electrons
that this shell can hold?
a)When n =3, ℓ values are 0, 1, 2
The mℓ values for each of this ℓ values are:

For ℓ= 0, mℓ = 0 (1 orbital)
For ℓ= 1, mℓ = -1, 0, +1 (3 orbitals)
For ℓ= 2, mℓ = -2, -1, 0, 1, 2 (5 orbitals)
Total number of orbitals is 1 + 3 + 5 = 9 orbitals
• To calculate the total number of orbitals in a shell
(n) one can thus use the formula: n2 = if n=3, there
32 orbitals = 9 orbitals.

b) Each orbital hold maximum of two electrons, if

there are 9 orbitals then no. of electrons = 9 × 2 = 18
The maximum number of electrons a shell can hold
is given by 2n2, 2(32) = 2(9) = 18
 Practice exercise

1) Complete the Table

Number of Max. number

n ℓ Subshell Orbitals of electrons
1 1 2
2s
2
1
2) Give the values of the quantum numbers associated with
orbitals in a 5d subshell.
n = 5, ℓ = 2 mℓ = – 2, – 1, 0, 1, 2 ms =
s Orbitals
Atomic Orbitals

• Value of ℓ = 0
 Spherical in shape

 Radius of sphere increases

with increasing value of n
 p Orbitals
• Value of ℓ = 1
 Have two lobes with a node between
them- dumbbell shape
d Orbitals • Value of ℓ = 2

 Four of the five

orbitals have 4
lobes;
 the other resembles
a p orbital with a
doughnut around the
centre
Energies of Orbitals

• As the number of electrons

increases, so does the
repulsion between them.

 Therefore, in many-electron
atoms, orbitals on the same
energy level are no longer
degenerate.
 Practice Questions

1. Which one of the following is not a valid value for the

magnetic quantum number of an electron in a 5d
subshell?
(a) 2 (b) 3 (c) – 1 (d) 0
2. Which quantum number determines the energy of an
electron in a hydrogen atom?
(a) mℓ (b) ℓ (c) n (d) n & ℓ
3. The angular momentum quantum number is 3 in
________ orbitals.
(a) s (b) p (c) d (d) f
 Practice Questions

4. Which one of the following represents an impossible

set of quantum numbers for an electron in an atom?
(arranged as n, l, ml, and ms)

(a) 5, 4, - 3, 1/2
(b) 1, 0, 0, 1/2
(c) 2, 1, -1, -1/2
(d) 3, 3, 3, ½
 Practice Questions

1. Relative to electrons and energy states, what

does each of the four quantum numbers
specify?
2. (a) Give two important quantum-mechanical
concepts associated with the Bohr model of
the atom.
3. (b) Give two important additional
refinements that resulted from the wave-
mechanical atomic model.
 Practice Questions
1. List the values of n, l and ml for orbitals in the 4d subshell.
2. Give the values of the quantum numbers associated with the
orbitals in the 3p subshell.
3. What is the total number of orbitals associated with the principal
quantum number n=3?
4. What is the total number of orbitals associated with the principal
quantum number n=4?
5. Write the four quantum numbers for an electron in a 3p orbital.
6. Write the four quantum numbers for an electron in a 5p orbital.
7. What is the maximum number of electrons that can be present in
the principal level for which n= 3?
8. What is the maximum number of electrons that can be present in
the principal level for which n= 4?
9. An oxygen atom has a total number of eight electrons. Write the
four quantum numbers each of the eight electrons in the ground state.