ATOMIC

STRUCTURE
 BRIEF HISTORY OF DISCOVERY OF
ATOMS AND SUBATOMIC PARTICLES
The concept of atom was given by Hindu and Greek
Philosophers in early days.
 Around 700 B.C. Maharshee Kapila gave the concept of paramanu,
around 600 B.C. Maharshee Kanada, proposed that matter is composed
of minute individual particles called paramanus.

 Around 400 B.C. the concept of atomic character of matter was given by
Leucippus and was recorded by Democritus, according to them, every
matter is composed of tiny, discrete and indivisible particles called atoms.

 The word atom is derived from Greek word atomos (a=absence, tomos=
cut) which means indivisible or uncuttable.

 In 1808 A.D., John Dalton put forward 1st atomic theory of matter.

 Modern atomic theory is different from Daltons atomic theory.

 Dalton’s atomic theory
In 1808, John Dalton gave atomic theory on a scientific basis.
Main postulates of the Dalton’s atomic theory are:

i. All substances are made up of tiny, indivisible particles called

atoms.
. Atoms cannot be created, divided or destroyed during any
ii
chemical or physical change.
iii. Each element is composed of its own kind of atoms.
iv. Atoms of different elements differ in mass and properties
Atoms combine with each other in simple whole number ratios to
v.
form compound atoms
Study of electric discharge through gas at low pressure, study
of radioactivity, confirmed that atom consists of number of
subatomic particles.
The electrical nature of matter was found when glass or ebonite rod
were rubbed with silk or fur.

The first direct evidence of the existence of subatomic

particles came from the Faraday’s electrolysis. In 1830, when
electricity is passed through electrolytic solution, there is
liberation or deposition of matter on corresponding
electrodes. The interaction between matter and electricity
further gives idea about the electrical nature of matter.

Discovery of electron: In 1897, J.J. Thomson discovered

electron from Discharge tube experiment.
 Figure2: Deflection of cathode rays

Figure1: Production of cathode rays

Discharge tube i.e a glass tube containing two electrodes (electrodes are metal plates and
metal consist of electrons) connected to a high voltage source (10,000V) and a high vacuum
pump. Pressure was reduced to o.oo1 mm Hg. When electric current is passed on tube, a
beam of current travelled in a straight lines from cathode to anode.

Cathode rays is independent of nature of the gas in the discharge

tube. They are made up of electrons and electrons are universal
constituents means they are same for every gas i.e nature of
electron is same.
 Properties of Cathode rays
Cathode rays are streams of negatively charged
particles called electrons.

They travel in a straight line and produce sharp

shadows of the object placed in their path.

Cathode rays are deflected by electric field towards the

positive plate, which shows that cathode rays are
composed of negatively charged particles.

Cathode rays when subjected to magnetic field, they

are deflected to a particular direction.

Cathode rays have velocity upto 1/10th of velocity of

light.
By studying the degree of deflection of cathode rays in
different magnetic and electric fields, the charge to mass
ratio(e/m) of an electron was determined by the J.J
Thomson’s experiment. e/m=1.76 ×108 coulomb/gram
Mullikan’s oil drop experiment gave the electric charge (e) of
an electron in 1909 which is found to be 1.6 × 10-19 coulomb.

By combining experimental results of Thomson and Mullikan,

mass of electron was found to be
e/(e/m) = 1.6 × 10-19 coulomb/ 1.76 ×108 coulomb/gram= 9.09 x
10-28 g = 9.1 x 10-31 Kg

Mass of an electron is nearly equal to 1/1837 the mass of

hydrogen atom(mass of hydrogen atom=1.6 × 10-24g)
Discovery of the proton
Presence of negatively charged particle in an atom i.e. electron
suggested that there must be positively charged particle
because atom as a whole is electrically neutral.

Goldstein in 1866, while carrying out experiments with

discharge tube containing perforated cathode discovered
positive rays or anode rays and the properties of these rays
showed that they consisted of positively charged particles.

A new kind of rays streaming behind the cathode were found

and such rays were found to travel in opposite direction to
cathode rays. These rays consists of positively charged
particles called positive or anode or canal rays.

Mass of a proton: 1.67 x 10-27 Kg

Charge of a proton : +1.602 x 10-19 C
 Production of anode rays

Anode rays are made up of positive ion and these are

dependent of nature of gas present in the discharge tube
because positive ions differs for each gas i.e. In a
positive ion, number of proton is different.
When the tube is filled with hydrogen gas, then the mass
of positive particle was 1800 times that of electron.
When other gases are used, their mass seems to be whole
number multiple of mass observed with hydrogen gas.
 Characteristics of a Proton:

• Mass of a Proton: The relative mass of a proton is 1 u.

• Charge of a Proton: The charge of a proton is equal and
opposite to the charge of an electron. The absolute
charge of a proton is
1.6 × 10–19 coulomb of positive charge.
DISCOVERY OF NEUTRON

 The discovery of another subatomic particle by James Chadwick

in 1932.
 This particle is called neutron.
 The neutron is a neutral particle found in the nucleus of an atom.

Characteristics of a neutron:

Mass of a Neutron: The relative mass of a neutron is 1 u.

Charge of a Neutron: Neutron has no charge.
Discovery of Neutron

In 1932, James Chadwick discovered the neutron by

bombarding beryllium target with alpha particles from the
natural radioactive element Polonium.

4Be + 2He 6C 0n
9 4 12 1

Mass of a neutron: 1.67 x 10-27 Kg = 1 u

Production of neutrons
COMPARISION OF SUBATOMIC PARTICLES
• Key Points

• An atom is composed of two regions: the nucleus, which is

in the center of the atom and contains protons and
neutrons, and the outer region of the atom, which holds its
electrons in orbit around the nucleus.

• Protons and neutrons have approximately the same mass,

about 1.67 × 10-24 grams, which scientists define as one
atomic mass unit (amu) or one Dalton.

• Each electron has a negative charge (-1) equal to the

positive charge of a proton (+1).

• Neutrons are uncharged particles found within the nucleus.

• An atom is the smallest unit of matter that retains all of the
chemical properties of an element.
• Atoms combine to form molecules, which then interact to
form solids, gases, or liquids.
• For example, water is composed of hydrogen and oxygen
atoms that have combined to form water molecules.

Electrons are much smaller in mass than protons, weighing

only 9.11 × 10-28 grams, or about 1/1837 of an atomic mass
unit.
Therefore, they do not contribute much to an element’s
overall atomic mass. When considering atomic mass, ignore
the mass of any electrons and calculate the atom’s mass
based on the number of protons and neutrons alone.
• The number of electrons orbiting the nucleus is equal to the
number of protons inside the nucleus.

• So, in these atoms, the positive and negative charges cancel

each other out, leading to an atom with no net charge and is
electrically neutral.
#Atomic Number
• Neutral atoms of an element contain an equal number of
protons and electrons.
• The number of protons determines an element’s atomic
number (Z) and distinguishes one element from another.
• For example, carbon’s atomic number (Z) is 6 because it has
6 protons. The number of neutrons can vary to produce
isotopes, which are atoms of the same element that have
different numbers of neutrons. The number of electrons can
also be different in atoms of the same element, thus
producing ions (charged atoms). For instance, iron, Fe, can
exist in its neutral state, or in the +2 and +3 ionic states.
 Mass Number

• An element’s mass number (A) is the sum of the number of

protons and the number of neutrons.
• Mass number can be used to easily calculate how many
neutrons an element has by simply subtracting the number
of protons from the mass number.
• Protons and neutrons both weigh about one atomic mass
unit or amu.
• Isotopes of the same element will have the same atomic
number but different mass numbers.
• Atomic number, chemical symbol, and mass number of
Carbon has an atomic number of 6, and two stable isotopes
with mass numbers of 12 and 13, respectively. Its average
atomic mass is 12.11.
• Scientists determine the atomic mass by calculating the mean
of the mass numbers for its naturally-occurring isotopes.
• Often, the resulting number contains a decimal. For example,
the atomic mass of chlorine (Cl) is 35.45 amu because
chlorine is composed of several isotopes, some (the majority)
with an atomic mass of 35 amu (17 protons and 18 neutrons)
and some with an atomic mass of 37 amu (17 protons and 20
neutrons).
• Given an atomic number (Z) and mass number (A), you can
find the number of protons, neutrons, and electrons in a
neutral atom.

• For example, a lithium atom (Z=3, A=7 amu) contains three

protons (found from Z), three electrons (as the number of
protons is equal to the number of electrons in an atom),
and four neutrons (7 – 3 = 4).
 # What is an Isotope?
• Isotopes are various forms of an element that have the same
number of protons but a different number of neutrons.
• Some elements, such as carbon, potassium, and uranium,
have multiple naturally-occurring isotopes. Isotopes are
defined first by their element and then by the sum of the
protons and neutrons present.
• Carbon-12 (or 12C) contains six protons, six neutrons, and
six electrons; therefore, it has a mass number of 12 amu (six
protons and six neutrons).
• Carbon-14 (or 14C) contains six protons, eight neutrons, and
six electrons; its atomic mass is 14 amu (six protons and
eight neutrons).
• Isotopes do differ in their stability.
• Carbon-12 (12C) is the most abundant of the carbon isotopes,
accounting for 98.89% of carbon on Earth.
• Carbon-14 (14C) is unstable and only occurs in trace
amounts.

#Isobars:
 Isobars are atoms that have same atomic mass (Greek isos
equal + Greek baros weight) but different atomic numbers.
 Isobars have different atomic numbers because they have
different numbers of protons.
 They have the same atomic mass because they have just
enough neutrons to make the same total of nucleons.
ATOMIC MODELS
1. JJ Thomson’s Atomic model
2. Rutherford’s Atomic model
3. Bohr’s Atomic model
Atomic Models
• J.J Thomson’s atomic model (1898)
After the discovery of positively charged particles and
negatively charged particles, Thomson was the first person
who discovered atomic model. He considered an atom to be
sphere of uniform positive charge (protons) into which
negatively charged particles (electrons) were embedded just
like seeds in watermelon so this model is also called Thomson’s
watermelon model or plum pudding model.
 This model could not explain how a
positive charge hold the negatively
charged electron in atom.

 Could not explain the position of

nucleus.
# Rutherford’s atomic model
• In 1911 Rutherford performed α- particle scattering
experiment to locate electrons and protons in an atom.
• In this experiment, he bombarded a thin gold sheet with α-
particles ( +ve particles equivalent to He2+ ) which is
obtained from a radioactive substance.
• Three types of α- particle were observed after scattering
of atom contained in the gold foil:
i. Most of the α- particles passed straight through the
atom
ii. Some of the α- particles deflected making angle
smaller than 90○
iii. Very few α- particles were reflected back
 According to Rutherford model, an atom has
following properties:

•Most part of the atom remains empty.

•Atom consists of positively charged nucleus.

•The electrons revolve around the nucleus in a

circular path.
 WHAT IS ALPHA PARTICLE?

α-particles are shot out from radio active

elements with very high speed.
They are the nucleus of helium
atoms. It has a charge of +2 and mass
4 amu and represented by 𝟐𝟐He4.
Conclusion
•Most of the α- particles passed through foil
undeflected, it means most of the space inside the
atom is hollow.
•There should be heavy positively charged body at
the centre of the atom as some of the α- particles
were deflected through different angles
•Since the number of α- particles deflected were
small, the positively charged body present within
the atom (i.e., nucleus) must be occupying a very
small volume.
•The diameter of the centre (nucleus) should be very
small ( radius 10-13 cm) in comparison of the atom.
• Rutherford proposed a nuclear model to an atom called as
Rutherford’s nuclear model of the atom.
1. An atom consists of +vely charged nucleus of radius
10-13 cm or 1 fermi
2. Atom is electrically neutral
 Limitations of alpha particle scattering
a. Could not explain the stability of atom.
Electrons and protons are held together by columbic force of
attraction. If an electron moves freely around the nucleus it
should radiates energy and gradually undergoes spiral motion
to fall into the nucleus within 10-8 sec and should collapse in
the nucleus of the atom but actually this doesn’t happen.
Atom exists because matter exists, so electrons never collapse
into the nucleus why? Not answered by this theory.
b. Radiation of energy by moving electron should give
continuous atomic spectra but this doesn’t happen as atoms
give discontinuous line spectra which represent radiation of
different frequencies. Rutherford model does not explain the
origin of line spectrum of hydrogen.
# Bohr’s atomic model (Based on partly on
Rutherford model and partly on Plancks Quantum
theory)

Thomson’s atomic model and Rutherford’s atomic

model failed to answer any questions related to the energy
of an atom and its stability.

 In the year 1913, Niels Bohr proposed an atomic

structure model, describing an atom as a small, positively
charged nucleus surrounded by electrons that travel in
fixed circular orbits around the positively charged nucleus
as planets around the sun in our solar system, with
attraction provided by electrostatic forces, popularly
known as Bohr’s atomic model.

It was basically an improved version of Rutherford’s

atomic model overcoming its limitations.
 BOHR’S ATOMIC MODEL

Postulates (Assumptions)

1. Fixed permitted orbits

2. Stationary states

3. Stability of atom

4. Explanation for the hydrogen spectrum

5. Quantization of angular momentum

• Main Postulates of Bohr’s atomic model
1. Electrons revolve around the nucleus in certain permitted
orbit.
2. Angular momentum of the electron when it revolves
around the certain permitted orbit is equal to the integral
multiple of h/2π
Mathematically it can be expressed as

Where n = integer ( 1 , 2, 3, …… denotes no.of shell or

orbit)
h = plank’s constant (6.624 × 10-27 erg-seconds)
m = mass of electron
v= velocity of electron
r = radius of orbit of electron
This principle is called a quantization principle.
3. Electrons revolve around the nucleus in stable orbits
without emission of radiant energy. Each orbit has a
definite energy and is called an energy shell or energy
level.
An orbit or energy level is designated as K, L, M, N
shells. When the electron is in the lowest energy level, it
is said to be in the ground state.
4. An electron emits or absorbs energy when it jumps from
one orbit or energy level to another.
When electron absorbs energy, electron jumps from a lower
energy level to a higher energy level and when electron
jumps from a higher energy level to lower energy level it
emits energy.
• The energy absorbed or emitted is equal to the difference
between the energies of the two energy levels (E1, E2) and
is determined by Planck’s equation.
ΔE = hv
Where, ΔE = E2-E1
ΔE = energy absorbed or emitted
h= Planck’s constant
v= frequency of electromagnetic radiation emitted or
absorbed
To explain the spectral distribution of energy emitted by a black
body, Max Planck in 1901 put concepts
a) Concept of Quantum (photon)
The emission or absorption of energy from light or any
electromagnetic radiation do not takes place continuously but
takes place discontinuously in the form of small packets of
energy called quanta. In case of light each quantum is called
photon.

b) Energy of quantum
Each quantum is associated with definite amount of energy
which is proportional to the frequency of radiation.

c) Quantization of energy
The amount of energy emitted or absorbed by a body is a whole
number multiple of quantum i.e. E=n*hᶹ
n must not be decimal or fractional, should be whole number.
Spectra simply means colour bands.
The arrangement of wavelength or frequency of radiations
in increasing or decreasing order is called spectrum.

The term spectrum was initially used to describe the

rainbow colour, produced on passing white light on prism.

The instrument used to separate radiations of different

wavelength is called spectroscope and the study of spectra
is called spectroscopy.
Continuous Spectrum
If a spectrum occurs in a wide range of wavelengths, without any
discontinuity, it is called continuous spectrum. E.g. Sunlight,
Rainbow colour, Flame of candle etc.

Discontinuous Spectrum
If a spectrum arises with some kind of discontinuity in the
wavelength, with in the range of spectrum, it is called discontinuous
spectrum. E.g. Hydrogen spectra
Emission Spectrum
If a light emitted from atoms/ molecules is passed through a prism
followed by a photographic plate, lines of selected colours of
different wavelength are observed, such spectra are called emission
spectra.

Absorption Spectrum
If a light is passed through a chemical substance, certain waves are
absorbed by atoms or molecules, then, light is passed through a prism
followed by photographic plate, continuous spectra having some dark
spaces are observed. Such spectra are known as absorption spectra.
ORIGIN OF LINE SPECTRUM OF HYDROGEN (BOHR’S
EXPLANATION)
Hydrogen Spectra
When an electric discharge is passed through
hydrogen gas at low pressure, hydrogen molecules
split into hydrogen atoms.
The electrons in different hydrogen atoms absorb a
different amount of energy and jump to different
energy levels. Since the lifetime of electrons in the
excited state is very short, electrons jump to lower
energy level or even to ground state in one or more
jumps by emitting electromagnetic radiation (photon)
and produce a large number of lines called spectral
series.
Depending on the wavelength of the radiation
emitted, 5 different types of spectral series are
observed.
Hydrogen Spectra
Hydrogen Spectra
•Limitations of Bohr Atomic Model Theory
It violates the Heisenberg Uncertainty Principle. The Bohr
atomic model theory considers electrons to have both a
known radius and orbit i.e. known position and momentum
at the same time, which is impossible according to
Heisenberg.

The Bohr atomic model theory made correct predictions

for smaller sized atoms like hydrogen, but poor spectral
predictions are obtained when larger atoms are considered.

It failed to explain the Zeeman effect when the spectral

line is split into several components in the presence of a
magnetic field.
 Defects of Bohr’s atomic model

1. No explanation for multielectron system

2. No explanation for hyperfine spectra

3. No explanation for Zeeman and Stark effect

4. No explanation for dual nature of electrons

5. Against Uncertainty principle

# Quantum Mechanical Model Of Atom
A. The de Broglie concept
In 1924, the French physicist, Louis de Broglie
suggested that if light were composed of particles and
waves, it should also be same for microscopic particles
(movable particles) like electron i.e. behaves both as a
material particle and as a wave. Hence called wave-
particle duality.
This presented a new wave mechanical theory of
matter. According to this theory, small particles like
electrons when in motion possess wave properties.
 According to de-Broglie , the wavelength associated
with a particle of mass m, moving with velocity v is
ℎ
given by the relation 𝜆𝜆 = where h = Planck’s
𝑚𝑚𝑚𝑚
constant.
•This can be derived as follows according to Planck’s
equation,
E = hv = h c/λ ∴ v = c/λ (energy of photon)
• on the basis of Einstein’s mass energy relationship)
E = mc2
Equating both,
hc/λ = mc2
or λ = h/mc
or λ = h/mv which is same as de-Broglie
relation. (∴ mv = p)
The de-Broglie equation is applicable to all material
objects but it has significance only in case of
microscopic particles.
de Broglie’s equation states as : The momentum of a
particle in motion is inversely proportional to its
wavelength, Planck’s constant ‘h’ being the constant of
proportionality.

The wavelength of waves associated with a moving

material particle (matter waves) is called de Broglie’s
wavelength.

The de Broglie’s equation is true for all particles, but it is

only with very small particles, such as electrons, that the
wave-like aspect is of any significance.
 (a) For a large mass
Consider a ball of mass 100 g moving with a velocity of
1000 cm/sec. The de Broglie’s wavelength λ will be given as
follows :

This is too small to be measurable by any instrument

and hence no significance.
 (b) For a small mass

Consider an electron in a hydrogen atom. It has a

mass = 9.1091 × 10– 28 g and moves with a velocity
2.188 × 10– 8 cm/sec. The de Broglie’s wavelength λ is
given as

This value is quite comparable to the wavelength of

X-rays (0.01 - 10 nm i.e. 10-8 to 10-12 m) and hence
detectable.
Heisenberg’s uncertainty principle
Due to the wave nature of the electron, it is not possible to measure
simultaneously both the exact position and momentum of electron.

Werner Heisenberg, gave principle about uncertainities in

simultaneous measurement of position and momentum of small
particles.
‘It is impossible to determine simultaneously both the exact
determination of the position and momentum (velocity) of
microscopic particle like an electron with absolute accuracy.’ This
principle is known as Heisenberg’s uncertainity principle.

Mathematically, if ∆x and ∆p are the uncertainties in the position

and momentum respectively then

∆x × ∆p ≥ h/4π
 Heisenberg’s Uncertainty Principle
• The exact and simultaneous determination of position
and momentum of a moving microscopic particle is
impossible at same time.
• If Δx and Δp are uncertainties in position and
momentum respectively, then
Δx. Δp ≥ h/4π
or, Δx. m Δv ≥ h/4π
or, Δx. Δv ≥ h/4πm
• If Δx is large, Δp is small, and vice versa. This means
that certainty in the measurement of one parameter
leads to the uncertainty in the measurement of other.
•Hence, uncertainty principle suggests that in an
atom, an electron does not always remain at a fixed
distance from the nucleus.

•It keep moving in whole space around the nucleus,

but tends to remain most of the time within a small
volume around the nucleus, where the probability
of locating electron is maximum.

•The probability concept gave an idea of atomic

orbitals, which provide wider space around the
nucleus for the movement of electrons.
Microscopic and Macroscopic Particles
∆x × ∆v ≥ h/4πm
∆x × ∆v ≥ 6.626 ×10-34/4 π × 9.1 ×10-31
≥ 5.79 ×10-5 (great error compared to mass of electron)
(More error less accuracy)
The value is extremely large and cannot be neglected. Hence for small
particles, we can’t determine the position and velocity simultaneously
with grat accuracy. That’s why Uncertainty principle is applied only for
small particles like electron, proton, neutron etc but not for large
particles.

∆x × ∆v ≥ 6.626 ×10-34/4 π × 1
≥ 5.27 × 10-35(small error compared to mass of large object)
OUTCOMES OF UNCERTAINITY PRINCIPLE (DAWN OF PROBABILITY
CONCEPT)
One of the most important outcome of uncertainity principle is
that the exact location of electron in an atom cannot be
determined.

If it is so, How to interpret the position of electron ? arise.

According to this principle, the probability of finding an electron
in an atom can be traced rather than its exact position.
Hence, the position of electron or such types of microparticles can
only be predicted on the basis of probability. It gave birth of
orbital concept.

An orbital is three dimensional space of an atom where the

probability of finding of electron is maximum.

Mathematically, if Ѱ is the wave function of electron, the probability

of finding an electron is given by Ѱ2
Quantum mechanical model of atom
The modern atomic structure is based on the wave nature of
electron, developed principally by L. de Broglie, W. Heisenberg and
E. Schrodinger
This model considers an atom as a positively charged nucleus,
surrounded by a stationary electron-wave extending in space around
the nucleus.

Features

1. It considers the wave like properties of electrons.

2. It emphasizes that the path of an electron in an atom

can never be known accurately.
3. It describes the state of an electron in an atom in terms
of the probability of finding it in the space around the
nucleus.
Schrodinger’s wave equation
To describe the mechanics of wave particle,
Schrodinger developed a mathematical equation in
1962.This concept is based on probability concept
and idea of electron as stationary wave (standing
wave) around the nucleus.

Ψ = wave function of moving electron

x, y and z = three space coordinates of electron
m= mass of electron
h= Planck’s constant
E=total energy of electron
V= potential energy of electron
DIFFERENCES BETWEEN ORBIT AND ORBITAL
The shapes and orientations of the s, p and d orbitals
are as shown in figure:-

Figure: Shapes and orientation of s, p and d orbitals.

Quantum Numbers
An atom possess a large no. of orbits and thus there is possibility of large
no. of orbitals.

These orbitals differ in size, shape, and orientation in space around

nucleus.

Each electron is quantized in an atom i.e. an electrons in an atom can hav

only certain permissible values of energy and angular momentum.
A set of four numbers which gives complete information about the state o
electron in an atom i.e. energy, orbital occupied, shape, size, orientation o
orbital and the direction of electron spin.

Quantum numbers are identification number of an electrons in an atom

through various aspects like its orbit, orbitals, orientation and mode of
movements etc.
•4types of quantum numbers:
I. Principal quantum number (n)
II. Azimuthal quantum number (l)
III. Magnetic quantum number (m)
IV. Spin quantum number (s)
I. The principal quantum number (n) describes the main
energy level or shell or orbit of an atom to which electron
belongs.
It is denoted by n indicating shell number starting from 1 to ∞.
The electron holding capacity of these shell can be calculated
by 2n2 rule.
It tells us about the number of subshells and number of
orbitals within the shell. For nth shell, nth subshell and n2
number of orbitals. For 3rd shell, n=3, it has 3 subshells (3s 3p
3d) and 9 orbitals (3s-orbital, 3Px, 3Py, 3Pz orbitals, 3dxy 3dyz
3dxz 3dx2-y2, 3dz2)
Principal Quantum Number ‘n’
Principal quantum number denotes the principal shell to which the
electron belongs. It is represented by ‘n’. It is also referred to as major
energy level. It represents the average size of the electron cloud i.e., the
average distance of the electron from the nucleus. This is, therefore, the
main factor that determines the values of nucleus-electron attraction, or
the energy of the electron.

The energy of the electron and its distance from the nucleus for
hydrogen atom are given by En = 13.6/ n2 eV/atom

and rn = 0.529 n2 Å
or, rn = 0.529 n2 * 10-10m

where n is the principal quantum number of the shell

The principal quantum number ‘n’ can have non-zero, positive, integral
values n = 1, 2, 3... increasing by integral numbers to infinity. Although
the quantum number ‘n’ may theoretically assume any integral value
from 1 to ∝ , only values from 1 to 7 have so far been established for the
atoms of the known elements in their ground states. An electron with n =
1 has the lowest energy and is bound most firmly to the nucleus.

The letters K, L, M, N, O, P and Q are also used to designate the energy

levels or shells of electrons with a n value of 1, 2, 3, 4, 5, 6, 7
respectively. There is a limited number of electrons in an atom which
can have the same principal quantum number and is given by 2n2, where
n is the principal quantum number concerned. Thus,
• Orbitals for which n = 2 are larger than those for
which n = 1, because they have opposite electrical
charges, electrons are attracted to the nucleus of the atom.

• Energy must therefore be absorbed to excite an electron

from an orbital in which the electron is close to the
nucleus (n = 1) into an orbital in which it is further from
the nucleus (n = 2). Let energies of 1,2,3,4,5 orbits be E1,
E2, E3, E4, E5

• The energy order can be E1 < E2 < E3 < E4 < E5

 Azimuthal or angular quantum number (l) also known
as subsidiary quantum number which describes about the
energy state of an electron in a subshell called as subenergy
level given by n+l rule. Lower n+l value indicates electrons
are first filled to that orbital.

Describes the shapes of the orbitals of a particular subshell.

Azimuthal quantum number was introduced by Sommerfeld
to account for the appearance of fine structures in hydrogen.

• Orbitals have shapes that are best described as spherical

(l = 0), polar (l = 1), or cloverleaf (l = 2). They can even
take on more complex shapes as the value of the angular
quantum number becomes larger.
•It can have only positive integral value from 0 to
(n-1), where n is principal quantum no.

•The spectroscopic terms sharp, principal, diffused

and fundamental are abbreviated as s, p,d and f
respectively.

•Tells about maximum number of electrons

permissible in a subshell given by 2(2l+1) and about
the number of orbitals permissible in a subshell
given by (2l+1)
Azimuthal Quantum Number ‘l’
Azimuthal quantum number is called secondary or subsidiary
quantum number. It defines the spatial distribution of the
electron cloud about the nucleus and describes the angular
momentum of the electron. In other words, the quantum
number l defines the shape of the subshell occupied by the
electron and the angular momentum of the electron.

Azimuthal quantum number l may have all integral values

from 0 to n – 1, each of which refers to an Energy sublevel or
Sub-shell. These sublevels are also symbolised by letters s, p,
d, f .

When principal quantum number n = 1, the only possible

value for l is 0 i.e., there is only one possible subshell i.e. s-
subshell (n = 1, l = 0).
For n = 2, there are two possible values of l, l = 0 and l = 2 – 1 = 1.

This means that there are two subshells in the second energy shell with
n = 2. These subshells are designated as 2s and 2p.

Similarly, when n = 3, l can have three values i.e. 0, 1 and 2. Thus

there are three subshells in third energy shell with designations 3s, 3p
and 3d respectively. For n = 4, there are four possible values of
azimuthal quantum number l (= 0, 1, 2, and 3) each representing a
different sublevel. In other words, the fourth energy level consists of
four subshells which are designated as 4s, 4p, 4d and 4f.
Thus for different values of principal quantum numbers we have

For a given value of principal quantum number the order of increasing energy
for different subshells is

s<p<d<f (except for H atom)

• Magnetic quantum number (m),is used to describe the
orientation a particular orbital in space. Magnetic number
was introduced to explain the Zeeman effects i.e. splitting
indicates subshells are further subdivided into regions
called orbitals.

• It is called the magnetic quantum number because the

effect of different orientations of orbitals was first
observed in the presence of a magnetic field.

• It is denoted by m and can have all integral value from –l

to + l including 0.

• + or – sign indicates one orientation and may hold a

maximum of two electron.
Magnetic quantum number is also called Orientation Quantum Number
because it gives the orientation or distribution of the electron cloud. It
gives the number of orbitals in a subshell.
For each value of the azimuthal quantum number ‘l’, the magnetic
quantum number ‘m’values between + l to – l includng zero

Thus when l = 0, m = 0 and no other value. This means that for each
value of principal quantum number ‘n’, there is only one orientation for l
= 0 (s orbital) or there is only one s orbital. For s orbital, there is only
one orientation, it must be spherically symmetrical about the nucleus.

There is only one spherically symmetrical orbital for each value of n

whose radius depends upon the value of n.

Figure: Spherical s orbitals, symmetrically disposed about the nucleus

For l = 1 (p orbital), the magnetic quantum number m will have three
values : + 1, 0 and – 1; so there are three orientations for p orbitals.

These three types of p orbitals differ only in the value of

magnetic quantum number and are designated as px, py, pz depending
upon the axis of orientation. The subscripts x, y and z refer to the
coordinate axes.

The p orbital are of dumb-bell shape consisting of two lobes. The two
lobes of a p orbital extend outwards and away from the nucleus along
the axial line. Thus the two lobes of a p orbital may be separated by a
plane that contains the nucleus and is perpendicular to the
corresponding axis. Such plane is called a nodal plane. There is no
likelihood of finding the electron on this plane.

For a px orbital, the yz plane is the nodal plane.

The shapes and orientations of the s, p and d orbitals are as shown in figure:-

Figure: Shapes and orientation of s, p and d orbitals.

For l = 2 (d orbital), the magnetic quantum number are five
(2 × 2 + 1); + 2, + 1, 0, – 1, – 2.

The five d orbitals are designated as dxy, dyz, dzx, dx2-y2 and
dz2 These orbitals have complex geometrical shapes as
compared to p orbitals.

When l = 3 (f orbital) the magnetic quantum number m can

have seven (2 × 3 + 1) values as + 3,+ 2, + 1, 0, – 1, – 2
and – 3. There are seven orientations. These seven orbitals
possess very complicated shapes and orientation in space.
Spin quantum number (s)
•Electrons behave as if they were spinning in
either a clockwise(↑) or anticlockwise (↓)
fashion.
•One of the electrons in an orbital is
arbitrarily assigned an s quantum number of
+1/2, the other is assigned an s quantum
number of -1/2.
•Thus, it takes three quantum numbers to
define an orbital but four quantum numbers
to identify one of the electrons that can
occupy the orbital.
Spin Quantum Number ‘s’
Spin quantum number represents the spin of electrons about their own
axis. Since an electron can spin clockwise or anticlockwise (in two
opposite directions), there are two possible values of s that are equal and
opposite. As quantum numbers can differ only by unity from each other,
1 1
there are two values given to s ; + and – depending upon whether the
2 2
electron spins in one direction or the other. Spins are also designated by
arrows pointing upwards and downward as ↓↑. Two electrons with the
same sign of the spin quantum numbers are said to have parallel spins
while those having opposite signs of the spin quantum numbers are said
to have opposite spin or antiparallel spin or paired-up spin.

Figure: Clockwise and anticlockwise spins of electrons about their own axis produce opposite magnetic fields.
After having concept of atomic orbitals and quantum numbers, the arrangement of electrons
in these orbitals of an atom is guided by 3 principles.
1. Aufbau principle
2. Hund’s rule of maximum multiplicity
3. Pauli’s exclusion principle
 Hund’s Rule of Maximum Multiplicity

Hund’s rule states that where orbitals are available in degenerate

sets, maximum multiplicity is preserved; i.e. electrons are not
paired until each orbital in a degenerate set has been half-filled.

This is an empirical rule that determines the lowest energy

arrangement of electrons in a subshell. It implies that pairing of
electrons in orbitals of p, d and f subshells does not take place till
each orbital belonging to that subshell has got one electron each.
Correct

e.g. Nitrogen has 1s2 2s2 2p3

configuration
Incorrect
Note: Since there are three p, five d and seven f orbitals,
the pairing of electrons in them would begin with the
4th, 6th and 8th electrons respectively. This is because
half-filled and completely filled states are associated
with extra stability.
 Pauli’s Exclusion Principle
Pauli’s Exclusion Principle

Three quantum numbers n, l and ml are needed to define an

orbital. Each orbital may hold up to two electrons, provided they
have opposite spins. An extra quantum number is required to
define the spin of an electron in an orbital. Thus, four quantum
numbers are needed to define the energy of an electron in an
atom. The Pauli exclusion principle states that no two electrons
in one atom can have all four quantum numbers the same. By
permutating the quantum numbers, the maximum number of
electrons which can be contained in each main energy level can
be calculated.
The maximum electron population per shell is shown below:-

This trend shows that the maximum electron population of a

shell is 2n2.

Writing Electronic Configuration

Electronic configuration of atoms is the distribution of electrons

into atomic orbitals. When atoms are in their ground state, the
electrons occupy the lowest possible energy levels.
• The half- filled d- orbital and full- filled d-orbitals are
more stable than other states of electronic configuration
• This is due to more symmetrical distribution of electron in
half and fulfilled orbital causes less electronic repulsion.
Hence lower the energy, greater will be stability, so
exchange of position by electron in half and fulfilled
orbitals which lowers the energy of system and increase
the stability.

 In order to write electronic configuration of ions, first

write down the electronic configuration of atom from
which ion is formed.
 Then remove the electrons from the outer most shell.
 e.g electronic configuration of Fe+3 ion is [Ar] 3d5
To show the positions of the electrons in an atom, the symbols 1s, 2s, 2p, etc. are used to
denote the main energy level and sublevel. A superscript indicates the number of
electrons in each set of orbitals. Thus for hydrogen, the 1s orbital contains one electron,
and this is shown as 1s1. For helium, the 1s orbital contains two electrons, denoted 1s2.

The electronic structures of the first few atoms in the periodic table may be written as
shown:-
An alternative way of showing the electronic structure of an atom is to draw
boxes for orbitals, and arrows for the electrons. By convention, electron spins are
represented by arrows pointing up (↑) or down (↓). The orbital diagram for
electronic configuration is more beneficial as all the four quantum numbers are
represented by it.
Explanation for Exceptions in Electronic Configuration in
COPPER AND CHROMIUM
The rules that we have learnt for predicting electron
configurations work most of the time, but not always.
However, determined electronic configuration of atoms reveals
that there are quite a few exceptions to the rules. For example,
two important exceptions are for chromium and copper.
Following the rules, we would expect the configurations to be

However, the actual electron configurations, determined experimentally, are

For chromium, an electron is “borrowed” from the 4s subshell to give a 3d

subshell that is exactly half-filled. For copper the 4s electron is borrowed to
give a completely filled 3d subshell. A similar thing happens with silver and
gold, which have filled 4d and 5d subshells, respectively.

Apparently, half-filled and completely filled subshells (particularly the latter) have
some special stability that makes such borrowing energetically favorable.
The stability of half-filled and completely filled subshells can be
attributed to the following two reasons:

1.The half-filled and completely filled shells have symmetrical

distribution of electrons, and therefore, are more stable as
symmetry is associated with greater stability.

2.When two or more electrons are present in degenerate orbitals

of a subshell with the same spin, they tend to exchange their
positions. The energy released during this exchange is known
as exchange energy. Electronic configurations with half-filled
shells permit maximum number of exchanges between
electrons of same spin, and thus maximum exchange energy is
released which contributes to the stability of the state.