Atomic Structure

FUNDAMENTAL PARTICLES

John Dalton (1766 – 1844), an English scientist developed in the years 1803 – 1808 his famous atomic
theory and suggested that the matter was made of extremely small indivisible particles called atoms.

The word atom is a Greek word meaning indivisible i.e., an ultimate

particle which cannot be further subdivided.

The work of J.J Thomson and Ernest Rutherford actually laid the foundation of the modern picture of the
atom.

It is now believed that the atom consists of several particles called sub-atomic particles like
electron, proton, neutron, positron, neutrino, meson etc. Out of these particles the proton,
electron and neutron are called fundamental particles and are the building
blocks of the atom.

DISCOVERY OF ELECTRON: CATHODE RAYS

The nature and existence of electron was established by experiments on conduction of
electricity through gases in a discharge tube.

The discharge tube : A discharge tube consists of a glass tube about one inch diameter and
perhaps two feet long and has metal plates embedded at the ends and is provided with a
vacuum pump.

The metal plates connected to a source of high voltage are called electrodes. If the electrodes
are separated by as much as two feet and the pressure in the discharge tube is decreased
progressively by removing the gas, a series of spectacular events occur.
Observation in discharge tube : An electric current begins to flow and at the
same time beautiful light through the gas between the electrodes are seen.

If the pressure is further reduced to 1/1,000,000 of an atmosphere, the light

disappears completely and there is only a greenish glow. If the gas pressure is
reduced still further, the current ceases to flow.

Conclusion : By a series of experiments, conducted mainly by the British physicist

J.J. Thomson, it was shown that originating near the cathode (negative electrode)
was a swiftly moving stream of charged particles which moved across the void
between the two electrodes.

These charged particles were first called cathode rays because of their origin at
the cathode; later they were given the name electrons by Stoney.
 Properties of Cathode Rays

Cathode rays possess the following properties:

(i) Cathode rays travel in a straight line:

Cathode rays cast shadow of the solid (mica cross) placed in
their path.

(ii) Cathode rays are made up of material particles:

When a light paddle wheel of mica mounted on an axle is
placed in the path of the cathode rays the wheel begins to
rotate on being hit by the electrons. This indicates that the
cathode rays are made up of material particles.

(iii) Cathode rays carry negative charge:

When an electric field is applied to a stream of cathode rays,
they are towards the positive plate of the electric field . This
indicates that cathode rays carry negative charges.

(iv) Cathode rays are deflected by magnetic field.

(v) Cathode rays produce heating effect:
When the cathode rays are allowed to strike a thin platinum
foil, it becomes red hot. This shows that cathode rays produce
heating effect.

(vi) Cathode rays produce X – rays:

The cathode rays when strike a hard metal surface (like
tungsten, molybdenum, platinum, copper etc.) produce X –
rays.
(vii) Cathode rays produce fluorescence:
The cathode rays produce faint greenish fluorescence on
striking the glass walls of the discharge tube or on striking zinc
sulphide or barium platinocyanide. The colour of fluorescence
light depends on the nature of substance.

(viii) Cathode rays ionize the gas through which they pass:
Cathode rays, on collision with the atoms of gases, can eject
electrons from them, and thus ionization of the gas occurs.

(ix) Cathode rays affect the photographic plates.

(x) Cathode rays penetrate through the thin foils of aluminium metal:
(xi) The charge to mass ratio (e/m) for the negatively charged particles in
the cathode is independent of the nature of the gas taken in the
discharge tube or the nature of the cathode.

DISCOVERY OF PROTON: ANODE RAYS (OR CANAL RAYS)

Atom is known to be electrically neutral. Since an atom contains negatively charged
electrons, it follows that some positively charged particles must also be present in it. The
first direct proof for the presence of positively charged particles in the atom was provided
by the discharge tube experiment conducted by Goldstein (1886) using perforated cathode.
On passing the electric discharge at a low pressure he observed a new type of rays
streaming behind the cathode. These are called anode rays or canal rays or positive rays and
produce green fluorescence on the opposite wall (i.e., behind cathode) of discharge tube.

Properties of Anode Rays

(i) Anode rays travel travel in straight lines.
(ii) Anode rays are made up of material particles.
(iii) Anode rays are deflected by electric field towards negatively charged plate. This
shows that anode rays consist of positively charged particles.
(iv) On applying a magnetic field in a direction perpendicular to the path of anode rays,
they get deflected in the direction expected for positive particles. This shows that
rays consist of positively charged particles.
(v) The e/m ratio of the particles in the anode rays depends upon the nature of the
taken in the discharge tube.
(vi) Like cathode rays, they also cause heating effect.
 Earlier Models of atoms
THOMSON MODEL OF ATOM

J.J. Thomson proposed in 1898 a model of the atom in which he assumed an atom as a
uniform sphere (radius approximately 10-13 cm) of positive electricity (i.e., positive charge)
in which electrons were embedded (just like the seeds in a watermelon) in such a way as
to give the most stable electrostatic arrangement.

In the Thomson’s model, The atom is visualized as a pudding or cake of positive charge
with raisins (electrons) embedded into it. This model is therefore, called “raisin pudding”
or “plum pudding model”.

The important features of this model are:

i. In this model the mass of the atom is considered to be evenly spread over the atom.
ii. This model could account for the electrical neutrality of the atom.
Limitation : Thomson’s model fails to explain the results of the alpha ray
scattering experiment carried out by Rutherford. This model was not able to
explain the overall neutrality of the atom.
 Discovery of neutron

 In 1932, James Chadwick observed that when beryllium bombarded with α-particles,
different kinds of particles were emitted.
 These particles had about the same mass as protons and carried no electrical charge.
 Hence, Chadwick named this particle as neutron.
RUTHERFORD’S MODEL
Rutherford allowed a narrow beam of 𝛼-particles to fall on a very thin gold foil of
thickness of the order of 4 × 10-4 cm and determined the subsequent of these particles
with the help of a zinc sulphide fluorescent screen. He found the following observations

Observation
i. Majority of the 𝛼-particles pass straight through the gold strip with or no deflection.
ii. Some 𝛼particles are deflected from their path and diverge.
iii. Very few 𝛼-particles are deflected backwards through angles greater than 90 o.
iv. Some were even scattered in the opposite direction at an angle of 180 o.

𝛼-particles emitted by radioactive substance were shown to be dipositive Helium ions

(He++) having a mass of 4 units and 2 units of positive charge.
 Atomic Model
On the basis of the above observation, Rutherford proposed an atomic model as follows

i. All the protons (+ve charge) and the neutrons (neutral charge) i.e., nearly the total mass
of an atom is present in a very small region at the centre of the atom. The atom’s central
core is called nucleus.
ii. The size of the nucleus is very small in comparison to the size of the atom. Diameter of the
nucleus is about 10-13 cm while the atom has a diameter of the order of 10-8 cm. So, the
size of atom is 105 times more than that of nucleus.
iii. Most of the space outside the nucleus is empty.
iv. The electrons, equal in number to the net nuclear positive charge, revolve around the
nucleus like planets revolve around the sun.

The zinc sulphide screen gives off a visible flash of light when struck by an 𝛼 particle, as
ZnS has the remarkable property of concerting kinetic energy of 𝛼 particle into visible
light. [For this experiment, Rutherford specifically used 𝛼 particles because they are
relatively heavy resulting in high momentum].
Atomic No. And Mass No.
Atomic no. of element is equal to total no of protons present in the nucleus or total no. of
electrons present in the neutral atom.

Mass no. of an element Is equal to sum of total no. of protons + no. of neutrons

Representation of a symbol with mass no. and atomic no,

Mass no. A

Symbol of element

Atomic no. Z
Isotopes:
Atoms of same element having same atomic number but different mass number,

1 2 3
e.g., H, H, H
1 1 1

Isobars:
Atoms of different elements (having different atomic no.) but same mass number are called
Isobars.

40 40
e.g., Ar , K
18 19

Isotones:
Atoms of different elements which contains same no. of neutrons,

14 15
e.g., C, N
6 7

Isoelectronics:
Atoms contains same no. electrons
e.g., O2- , F-

Isosteres :
are chemical species having a similar size, the same number of atoms
and valence electrons. Example : N2O and CO2

Isodiaphers :
A set of nuclides which has a different number of protons and neutrons but there exists the
same difference between the protons and neutrons are isodiaphers.

For example, Thorium -234( 144-90 =54) and Uranium -238 (146-92 = 54) are considered as
isodiaphers.
ELECTROMAGNETIC wave theory

Maxwell proposed that radiant energy (light) has wave characteristics.

Light according to him is Electromagnetic Wave arising due to the disturbance created by
electric and magnetic fields oscillating perpendicular to each other in space. Like all other
mechanical waves, it is characterised by velocity c, frequency v, wavelength 𝜆 which are related
as:

c = v 𝜆. The value of c is constant and equal to 3 × 108 m/s.

Wavelength:

It may be defined as the distance between any two consecutive crests or troughs. It is
represented by ⋋

Frequency:

It may be defined as the no. of waves passing through a point in one second it is represented by
υ.

Amplitude:

It is the height of the crest and depth of the trough.

ELECTROMAGNETIC SPECTRUM
Electromagnetic wave or radiation is not a single wavelength radiation, but a mixture of various
wavelength or frequencies. All the frequencies have same speed (=c).

If all the components of Electromagnetic Radiation (EMR) are arranged in order of increasing
wavelengths or frequencies, the pattern obtained is known as Electromagnetic Spectrum. The
following table shows all the components of light.

[Link]. Name Wavelength Frequency (Hz) Source

1. Radio wave 3 × 1014 – 3 × 107 1 × 105 – 1 × 109 Alternating current of high

frequency
2. Microwave 3 × 107 – 6 × 106 1 × 109 – 5 × 1011 Klystron tube

3. Infrared (IR) 6 × 106 – 7600 5 × 1011 – 3.95 × 1016 Incandescent objects

4. Visible 7600 – 3800 3.95 × 1016 – 7.9 × 1014 Electric bulbs, sun rays

5. Ultraviolet (UV) 3800 – 150 7.9 × 1014 – 2 × 1016 Sun rays, arc lamps with
mercury vapours
6. X-Rays 150 – 0.1 2 × 1016 – 3 × 1019 Cathode rays striking metal plate

7. 𝛾 - Rays 0.1 – 0.1 3 × 1019 – 3 × 1020 Secondary effect of radioactive

decay
8. Cosmic Rays 0.01 – zero 3 × 1020 – Infinity Outer space
PLANCK’S QUANTUM THEORY

When a black body is heated, it emits thermal radiations of different wavelengths or

frequency. To explain these radiations, Max Planck put forward a theory known as Planck’s
quantum theory. The main points of quantum theory are

(i) Substances radiate or absorb energy discontinuously in the form of small packets or
bundles of energy.
The smallest packet of energy is called quantum. In case of light the quantum. In
case of light the quantum is known as photon.
(ii) The energy of a quantum is directly proportional to the frequency of the radiation. E
∞ v (or) E = hv were v is the frequency of radiation and h is Planck’s constant having
the value 6.626 × 10-27 erg – sec or 6.26 × 10-34 J-sec.
(iii) A body can radiate or absorb energy in whole number multiples of a quantum hv,
2hv, 3hv …. Nhv where n is the positive integer.

Neil’s Bohr used this theory to explain the structure of atom.

PHOTOELECTRIC EFFECT
Hertz Lenard observed that when a clean metallic surface is irradiated by monochromatic light
of proper frequency, electrons are emitted from it.

This phenomenon of ejection of the electrons from surface of metal when light of suitable
frequency fall on it is called Photoelectric Effect.

It was observed that if the frequency of incident radiation is below a certain minimum value
(threshold frequency), no emission takes place however high the intensity of light may be.

Another important feature observed was that the kinetic energy of the electrons emitted is
independent upon intensity of light. The kinetic energy of the electrons increases linearly with
the frequency of incident light radiation.

This was highly contrary to the laws of Physics at that time i.e., the energy of the electrons
should have been proportional to the intensity of the light, not on the frequency.

These features could not be properly explained on the basis of Maxwell’s concept of light as
electromagnetic wave.

According to Einstein, when a quantum of light (photon) strikes a metal surface, it imparts its
energy to the electrons in the metal. In order for an electron to escape from the surface of the
metal, it must overcome the attractive force of the positive ions in the metal. So a part of the
photon’s energy is absorbed by the metal surface to release the electron, this is known as work
function of the surface and is denoted by ф. The remaining part of the energy of the photon
goes into the kinetic energy of the electron emitted. If E is the energy of the photon, KE is the
kinetic energy of the electron and ф be the work function of the metal then we have;
 ф = hvo and Ei = hv

⟹ KE = Ei – ф ⟹ KE = hv – hv0 = h (v – v0)

Also, if m be the mass and v be the velocity of the electron ejected then

KE = ½ mv2 = h (v – v0)

Note: the electromagnetic Radiation (or wave) now emerges as an entity which shows dual
nature i.e., sometimes as wave and sometimes as Particle (quantum aspect).

BLACK BODY RADIATION

In 1900, Max Planck was the first to give a clear explanation for the phenomenon of black body
radiation. According to the Max Planck theory, an ideal body is a perfect absorber and perfect
emitter of radiation and is called a black body. The radiation emitted by such a body is called
black body radiation.

When such a body is heated, it emits radiation over a wide range of wavelengths.

For example, when an iron rod is heated in a furnace, it first turns to dull red and then
progressively becomes more and more red as the temperature increases. On heating further,
the radiation emitted becomes white and then blue as the temperature becomes very high. In
terms of frequency, it means that the radiation emitted goes from a lower frequency to a
higher frequency as the temperature increases. The red colour lies in the lower frequency
region while the blue colour belongs to the higher frequency region of the electromagnetic
spectrum. The exact frequency distribution of the emitted radiation (i.e., intensity versus
frequency curve of the radiation) from a black body depends only on its temperature.

Note : At a given temperature, the intensity of radiation emitted increases with a decrease in
wavelength, reaches a maximum value at a given wavelength, and then starts decreasing with
further decrease in wavelength, as shown in Fig.
The above experimental results cannot be explained satisfactorily on the basis of the wave
theory of light. In 1900, Max Planck provided an explanation for this behaviour. He said that
atoms and molecules could emit (or absorb) energy only in discrete quantities and not in an
arbitrary amount or in a continuous manner as was believed till then. Planck gave the name
quantum to the smallest quantity of energy that can be emitted (or absorbed) in the form of
electromagnetic radiation.

SPECTRA : Arrangement of radiations in order of increasing wavelengths or decreasing frequencies.

Types of spectra

1. Emission
2. absorption

Type of Emission spectra

Continuous Spectrum

When sunlight (white light) is passed through a prism, it is dispersed or resolved into continuous spectra
of colours. It extends from RED (7600 Å) at one end to the VIOLET (3800 Å) at other end. In this region,
all the intermediate frequencies between red and violet are present. The type of spectrum is known as
continuous spectrum., Hence continuous spectra is one which contains radiation of all the frequencies.
Discontinuous Spectrum

Light emitted from atoms heated in a flame or excited electrically in gas discharge tube, does not
contain a continuous spread of wavelengths (or frequencies). It contains only certain well defined
wavelength (or frequencies). The spectrum pattern appears as a series of bright lines (separated by gaps
of darkness) and hence called as Line-Spectrum.

One notable feature observed is, that each element emits a characteristic spectrum, suggesting that
there is discrete relation between the spectrum characteristics and the internal atomic structure of an
atom.

ATOMIC SPECTRUM

If the atom gains energy the electron passes from a lower energy level to a higher energy level, energy is
absorbed that means a specific wave length is absorbed. Consequently, a dark line will appear in the
spectrum. This dark line constitutes the absorption spectrum.

If the atom loses energy, the electron passes from higher to a lower energy level, energy is released and
a spectral line of specific wavelength is emitted. This line constitutes the emission spectrum.

Spectrum of Hydrogen Atom

If an electric discharge is passes through hydrogen gas taken in a discharge tube under low pressure, and
the emitted radiation is analysed with the help of spectrograph, it is found to consist of a series of sharp
lines in the UV, visible and IR regions.

This series of lines is known as line or atomic spectrum of hydrogen. The lines in the visible region can
be directly seen on the photographic film.
Each line of the spectrum corresponds to a light of definite wavelength. The entire spectrum consists of
six series of lines each series, known after their discoverer as the Balmer, paschen, Lyman, Brackett,
Pfund and Humphrey series. The wavelength of all these series can be expressed by a single formula.

1 1 1
𝜆
=v=R 𝑛12
- 𝑛2 z2
2

v = wave number

𝜆 = wave length

R = Rydberg constant (109677 cm-1) or 1.09677 × 107 m-1

1/R= 911.5Ao

n1 and n2 have integral values as follows

Series n1 n2 Main spectral lines

Lyman 1 2, 3, 4, etc Ultra-vio

Balmer 2 3, 4, 5 etc Visible

Paschen 3 4, 5, 6 etc Infra – red

Brackett 4 5, 6, 7 etc Infra – red

Pfund 5 6, 7, 8, etc Infra – red

The pattern of lines in atomic spectrum is characteristic of hydrogen.

BOHR’S ATOMIC MODEL
Bohr developed a model for hydrogen like one-electron species. He applied Planck’s quantum
theory in considering the energy of an electron bound to the nucleus.

Important postulates

 An atom consists of a dense nucleus situated at the centre with the electron revolving
around it in circular orbits without emitting any energy.
The force of attraction between the nucleus and an electron is equal to the centrifugal
force of the moving electron.
 Of the finite number of circular possible around the nucleus, an electron can revolve
only in those orbits whose angular momentum (mvr) is an integral multiple of factor h/2
𝜋
𝑛ℎ
mvr = 2 𝜋

where, m = mass of the electron

v = velocity of the electron
n = orbit number in which electron is present
r = radius of the orbit
 As long an electron is revolving in an orbit it neither loses nor gains energy. Hence these
orbits are called stationary states. Each stationary state is associated with a defined
amount of energy and it is also known as energy levels. The greater the distance of the
energy level from the nucleus, the more is the energy associated with it. The different
energy levels are numbered as 1, 2, 3, 4, (from nucleus onwards) or K, L, M, N etc.

 If energy is supplied to an electron, it may jump (excite) instantaneously from lower

energy (say 1) to higher energy level (say 2, 3, 4, ertc.) by absorbing one quantum of
energy. This new state of electron is called as excited state. The quantum of energy
absorbed is equal to the difference in energies of the two concerned levels.

Since the excited state is less stable, atom will lose ‘it’s energy and come back to the
ground state. Thus energy is emitted when electron come back to ground state or
excited state to lower state.
 Energy released in an electron jump, ( ∆ 𝐸) is given by
∆ E = E 2 – E1 = h v
Where E2 and E1 are the energies of the electron in the first and second energy levels,
and v is the frequency of radiation absorbed or emitted.

Merits of Bohr’s Theory

(i) The experimental value of radii and energies in hydrogen atom are in good
agreement with that calculated on the basis of Bohr’s theory.
(ii) Bohr’s concept of stationary state of electron explains the emission and absorption
spectra of hydrogen like atoms.
(iii) The experimental values of the spectral lines of the hydrogen spectrum are in close
agreement with the calculated by Bohr’s theory.
 Energies can be given by:-
2𝜋 2 𝑚𝑒 4
En = - 𝑛2 𝑛2
Substitute value of m , e and h :-
2.18 ×10−19
En = - J/atom
𝑛2
For H- like particles:-
1312 𝑍 2
En = - 𝑛2 KJ/mol
Radii of the stationary states can be given by:-
0.529𝑛2
rn = 𝑧

Velocity can be given by :-

𝑍
Vn = V o × 𝑛 where Vo = 2.18× 108 cm/s

Limitations
(i) It does not explain the spectra of atoms or atom or ions having more than one
electron.
(ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman
Effect) or electric field (Stark effect) on the spectra of atoms or ions. It was observed
that when the source of a spectrum is placed in a strong magnetic or electric field,
each spectral line further splits into a number of lines This observation could not be
explained on the basis of Bohr’s model.
(iii) de Broglie suggested that electrons like light have dual character. It has particle and
wave character. Bohr treated the electron only as particle.
(iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty Principle.

According to this principle ‘’It is impossible to determine simultaneously the exact

position and momentum of a small moving particle like an electron’’. The
postulate of Bohr, that electrons revolve in well defined orbits around the nucleus
with well defined velocities is thus not attainable.
DUAL CHARACTER

Idea

In case of light some phemomenon like diffraction and interference can be explained on the
basis of its wave character. However, the certain other phenomenon such as black body
radiation and photoelectric effect can be explained only on the basis of its particles nature.
Thus, light is said to have a dual character. Such studies on light ware made by Einstein in 1905.

Louis de Broglie, in 1924 extended the idea of photons to material particles such as electron
and he proposed that matter also has a dual character-as wave and as particle.

Derivation of de-Broglie equation

The wavelength of the wave associated with any material particle was calculated by analogy
with photon. In case of photon, if it is assumed to have character, its energy is given by

E = hv …. (i) (assumed to the Planck’s quantum theory)

Where v is the frequency of the wave and ‘h’ is Planck’s constant

If the photon is supposed to have particle character, its energy is given by

E = mc2 … (ii) according to Einstein’s equation)

Where ‘m’ is the mass of photon, ‘c’ is the velocity of light.

By equation (i) and (ii)

h v = mc2
but v = c/𝜆
𝑐
h 𝜆 = mc2
(or) 𝜆 = h/mc

The above equation is applicable to material particle if the mass and velocity of photon is
replaced by the mass and velocity of material particle. Thus for any material particle like
electron.
ℎ
𝜆 = h/mv (or) 𝜆 = 𝑝

Where mv = p is the momentum of the particle.

HEISENBERG’S UNCERTAINTY PRINCIPLE

This principle states “It is Impossible to measure simultaneously the position and momentum of
a small microscopic moving particle with absolute accuracy or certainty i.e., if an attempt is
made to measure any one of these two quantities with higher accurancy, the other becomes
less accurate.”

Thus ,the mathematical expression for the Heisenberg’s uncertainty principle is simply written
as

Explanation of Heisenberg’s uncertainty principle

Suppose we attempt to measure both the position and momentum of an electron, to pinpoint
the position of the electron we have to use light so that the photon of light strikes the electron
and the reflected photon is seen in the microscope. As a result of the hitting, the position as
well as the velocity of the electron are disturbed. The accuracy with which the position of the
particle can be measured depends upon the wavelength of the light used. The uncertainty in
position is + 𝜆. The shorter the wavelength, the greater is the accuracy. But shorter wavelength
means higher frequency and hence higher energy. This high energy photon on striking the
electron changes its speed as well as direction. But this is not true for macroscopic moving
particle. Hence Heisenberg’s uncertainty principle is not applicable to macroscopic particles.
QUANTUM MECHANICAL MODEL OF ATOM

The atomic model which is based on the particle and wave nature of the electron is known as
wave or quantum mechanical model of the atom. This was developed by Schrodinger in 1926.
This model describes the electron as a three dimensional wave in the electronic field of
positively charged nucleus. Schrodinger derived an equation which describes wave motion of
an electron.

The differential equation is

𝒅𝟐 𝜳 𝒅𝟐 𝜳 𝒅𝟐 𝜳 𝟖 𝝅𝟐 𝒎
+ + + (E – V) Ψ = 0
𝒅𝒙𝟐 𝒅𝒚𝟐 𝒅𝒛𝟐 𝒉𝟐

Where x, y, z are certain coordinates of the electron, m = mass of the electron, E = total energy
of the electron. V = potential energy of the electron; h = planck’s constant and Ψ (psi) = wave
function of the electron.

Significance of Ψ:
The wave function may be regarded as the amplitude function expressed in terms of
coordinates x, y and z. the wave function may have positive or negative values depending upon
the value of coordinates.

The main aim of Schrodinger equation is to give solution for probability approach. When the
equation is solved, it is observed that for some regions of space the value of Ψ is negative. But
the probability must be always positive and cannot be negative, it is thus, proper to use Ψ2 in
favors of Ψ.

Significance of Ψ2:
Ψ2 is a probability factor. It describes the probability of finding an electron within a small space.
The space in which there is maximum probability of finding an electron is termed as orbital.

The important point of the solution of the wave equation is that it provides a set of number
called quantum numbers which describe energies of the electron in atoms, information about
the shapes and orientations of the most probable distribution of electrons around nucleus.

QUANTUM NUMBERS
Before understanding the concept of quantum no. we must know the following terms

Energy level

The non-radiating energy paths around the nucleus are called as energy levels of shells. These
are specified by numbers having values 1, 2, 3, 4,… or k, L, M,N,… in order of increasing
energies. The energy of a particular energy level is fixed.
Sub-energy Level

The phenomenon of splitting of spectral lines in electric and magnetic fields reveals that there
must be extra energy levels within a definite energy level. These were called as sub-energy level
or sub- shells. There are four types of sub-shells namely; s, p, d, f.

Orbital:

Each sub-energy level (sub-shell) is composed of one or more orbitals. These orbitals belonging
to a particular sub-shell have equal energies and are called as degenerate orbitals.

s-Sub-shell has one orbital, p has three orbitals, d have five orbitls and f has seven orbitals.

To describe or to characterize the electrons around the nucleus in an atom, a set

of four numbers is used, called as quantum numbers. These are specified such
that the states available to the electrons should follow the laws of quantum
mechanics or wave mechanics

Principal Quantum Number: (n)

a. This quantum number represents the main energy levels (principle energy levels)
designated as n = 1, 2, 3, … of the corresponding shells are named as K, L, M, N, …
respectively.
b. It gives an idea of position and energy of an electron. The energy level n = 1
corresponds to minimum energy and subsequently n = 2, 3, 4, … are arranged in order of
increasing energy.

Higher is the value of n, greater is its distance from the nucleus, greater is its size and also
greater is its energy.

c. It also gives the total electrons(2n2) that may be accommodated in each shell.

Azimuthal Quantum Number or angular quantum no. or subsidiary quantum no.

(𝒍)
This quantum number tells about no. of subshells in the main energy level and determines the
shape of the electron cloud.

For a given value of n, l has values from 0 to n – 1.

Each value of l describes a particular sub-shell in the main energy level and determines the
shape of the electron cloud.

When n = 1, l = 0, i.e., its energy level contains one sub-shell which is called as a s-subshell. So
for l= 0, the corresponding sub-shell is a s-sub-shell. Similarly when l = 1, 2, 3, the sub-shells are
called p, d, f sub-shells respectively.

𝒉
The orbital Angular momentum of electron = √𝒍(𝒍 + 𝟏) .
𝟐𝝅

Magnetic Quatum Number (m)

Concept:

An electron with angular momentum can be thought as an electric current circulating in a loop.
A magnetic field due to this current is observed. This induced magnetism is determined by the
magnetic quantum number. Under the influence of magnetic field, the electrons in a given sub-
energy level prefer to orient themselves in certain specific regions in space around the nucleus.

This quantum number tells about the number of possible orientations for a sub-energy level.
For a given value of l, m can have any integral values between - l to + l including 0 .

In s sub-shell there is only one orbital [ l= 0, ⇒ m = (2 l + 1) = 1 ].

In p sub-shell there are three orbitals corresponding to three values of m: -1, 0 + 1. [ Ι = 1 ⇒ m =

(2𝑙+ 1) = 3]. These three orbitals are represented as px , py , pz along X, Y, Z axes perpendicular
to each other.

In d sub-shell, there are five orbitals corresponding to -2, -1, 0 + 1, +2, [1 = 2 ⇒ = ( 2 × 2 + 1 ) = 5

]. These five orbitals are represented as dxy , dyz , dzx , dx2 – y2 , dz2.

Spin quantum Number (s)

When an electron rotates around a nucleus it also spins about its axis. If the spin is clockwise,
its spin quantum number is + ½ and is represented as ↑ . If the spin is anti-clockwise, its value is
– ½ and is represented as ↓ .
AUFBAU PRINCIPLE ( filling of electron in subshells)
Aufbau is a german word meaning bulding up.’

Acc. to this “electrons are filled in various subshells of a shell in increasing order
of their energies”

1s, 2s, 2p, 3s, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p.
n+l rule
The sequence in which various subshells are filled up can also be determined with the help of (n
+ l) value.

For a given subshell. The subshell with lowest (n + l) value is filled first.

When two or subshells have same (n + l) value, the subshell with lowest value of ‘n’ is filled
up first.

Exceptions to Aufbau Principle

In some case it is seen that actual electronic arrangement is slightly different from arrangement
given by Aufbau principle. A simple reason behind this is that half-filled and full filled subshells
have got extra stability.

Cr (24) ⟶ 1s2 , 2s2 2p6 , 3s2 3p6 3d4 , 4s2 (wrong)

⟶ 1s23 , 2s2 2p6 , 3s2 3p6 3d5 , 4s1 (right)

Reason of extra stability

1. Symmetrical distribution of electrons
2. Higher exchenge energy
Greater the number of exchanges higher will be the exchange energy more will the
stability.
Cu (29) ⟶ 1s2 , 2s2 2p6 , 3s2 3p6 3d9 , 4s2 (wrong)

⟶ 1s2 , 2s2 2p6 , 3s2 3p6 3d10 , 4s1 (right)

Similarly the following elements have slightly different configurations than expected.

Nb ⟶ [ Kr ] 4d4 5s1

Mo ⟶ [ Kr ] 4d5 5s1

Ru ⟶ [ Kr ] 4d7 5s1

Rh ⟶ [Kr ] 4d8 5s1

Pd ⟶ [ Kr ] 4d10 5s0

Ag ⟶ [ Kr ] 4d10 5s1

Pt ⟶ [Xe ] 4f14 5d9 6s1

Au ⟶ [ Xe ] 4f14 5d10 6s1

Pauli’s Exclusion Principle :

According to this principle “No two electrons in an atom can have the same set of all the
quantum numbers.”

Consider an electronic arrangement in 1st energy level (n = 1). For n = 1. 1 = 0, and m = 0. Now s
can have two values corresponding to each value of m i.e. s = + ½ - ½ (n, l, possible designation
of an electron in a state with n = 1 is 1, 0, 0, + ½ and 1, 0, 0, - ½ (n, 1, m, s) i.e., two quantized
states.

This implies that an orbital can accommodate (for n = 1, m = 0, ⇒ one orbital) maximum of two
electrons having opposite spins.
The maximum number of electrons in the different subshells = 2(2l + 1)

s-sub-shell = 2, p-sub-shell = 6, d-shell = 10 and f-sehll = 14.

Hund’s Rule of maximum Multiplicity

According to this rule:

“ Pairing of electron in an atomic orbital cannot take place until each orbital of that subshell
contain one electron each.”

By doing this, the electrons stay as far away from each other as possible. This is highly
reasonable if we consider the electron-electron repulsion. Hence electrons obey Hund’s rule as
it results in lower state and hence more stability.
Shapes of Atomic Orbitals

(i) S-orbital:

The s-orbital is said to spherically symmetrical about the nucleus, so that the
electronic charge is not concentrated in any particular direction.

(ii) p-orbitals:
There are three p-orbitals : px , py and pz. They are dumb-bell shaped, the two levels
being separated by; a nodal plane, i.e., a plane where the probability of finding
electron is zero.
 The p-orbitals have a marked direction character, depending as whether px , py and
pz orbital is being considered. The p-orbitals consist of two lobes with the atomic
nucleus lying between them. The axis of each p-orbital is perpendicular to the other
two. The px ,py and pz orbitals are equivalent except for their directional property.
They have the same energy( orbitals having the same energy are said to be
degenerated.)

(iii) d-orbitals : There are five d-orbitals. The shapes of d-orbitals resemple four leaf
cloves. dz2 has doughnut shape.
There are 2 nodal planes in each d orbital except dz2 where there is no
nodal plane.

NODE AND NODAL PLANE

Node is defined as a region where the probabity of finding an electron is zero.
The planes passing through the angular nodal points are called nodal planes.

Nodes:
No. of radial or spherical nodes = n - l - 1

No. of angular nodes = /, Total no. of nodes = n -1

Nodal planes in d orbitals. dz2 has no any nodal planes.

Planar nodes in p orbitals