UNIT-2

ATOMIC STRUCTURE
The concept of atom was first introduced by John Dalton in 1808. His theory called “Dalton’s
atomic theory” regarded atom as the smallest indivisible particle of matter.

Later at the end of 19th century the experimental evidences obtained by scientists like J.J
Thomson, Rutherford, Chadwick and many others proved the internal structure of atom. They found that
atoms are made up of fundamental particles like electrons, protons and neutrons.

Discovery of electrons – Cathode rays

The information about electrons was obtained from the study of cathode rays. Cathode rays were
obtained by discharge tube experiments done by scientists mainly Faraday in mid 1850s.

Discharge tube is a long glass tube fitted with two metal electrodes on either ends. The tube is also
connected to a vacuum pump for controlling the pressure of the gas inside the tube.

Gases are poor conductors of electricity

under ordinary pressure. However, if a high
voltage (10000 volts) is applied under low
pressure, they become conducting. Also a stream
of particles starts moving in the tube from cathode
to anode. Since these rays originated from the
cathode, these rays are called cathode rays.
J.J. Thomson studied the nature and
properties of these rays. He found that these rays
consist of negatively charged particles. He called
them electrons.

Results of discharge tube experiment [Properties of cathode rays].

1. Cathode rays start from cathode and move towards anode.

2. In the absence of electric and magnetic fields, cathode rays travel in straight line.
3. They can rotate light paddle wheel placed in their path. This shows that cathode rays consist of
material particles, which can produce mechanical motion.
4. They are deflected towards positive plate in an electric field. This shows that cathode rays consist
of negatively charged particles.
5. They are also deflected in a magnetic field.
6. They produce fluorescence when falls on certain fluorescent or phosphorescent materials.
7. Cathode ray ionizes the gases through which they pass.
8. They produce X-rays when fall on metals such as tungsten, copper etc.
9. The charge and mass of the particles in the cathode ray is independent of the nature of the gas
inside the tube. Thus we can conclude that electrons are basic constituent of all the atoms.

Charge to mass ratio (e/m) of electrons

The charge to mass (e/m) ratio for electron was determined by J.J Thomson. The value of e/m was
found to be 1.758 x 108 coulombs/g (1.758 x 1011 coulombs /kg)
He determined the e/m ratio by using cathode ray tube by applying electrical and magnetic fields
perpendicular to the path of electrons. The deviation of particles from the path depends on the following
factors.
1. Charge on the particle: Greater the charge, greater is the deflection.
2. The mass of the particle: Lighter the particle , greater is the deflection.

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 3. The strength of electric or magnetic field: Higher the strength, greater is the deflection.

When only electric field is applied electron deviate

from the path and strikes at the point A. Similarly when
magnetic field is applied, electron strike at point C. By carefully
balancing electric and magnetic fields, it is possible to bring
back the electrons at point B

From the careful measurement of the amount of

deflection and strength of electric field and magnetic field, it is
possible to calculate e/m ratio of an electron

Charge of the electron

The charge of the electron was determined by R.A. Millikan in 1909 by “ oil drop experiment”.
The charge was found to be 1.6 x 10-19 C. This is taken as one unit negative charge.

Millikan’s oil drop experiment

In this method, tiny oil drops produced by an atomizer is

allowed to fall through a tiny hole in the upper plate of electrical
condenser. These droplets are then viewed through a telescope.
From the rate of fall it is possible to calculate the mass of oil
drops. Then the air inside the chamber is ionized by passing a
beam of X-rays. Then the oil drops gain charge on their surface.
As a result the fall of these droplets can be retarded, accelerated
or made stationary depending on the charge. By carefully
measuring the effects of electrical field strength on the motion of
oil drops, it is possible to calculate the magnitude of electrical
charge on the drop. Millikan found that the charge is always an
integral multiple of 1.6 x 10-19 C. So he concluded that charge of
an electron is 1.6 x 10-19 C.

Mass of electron

By combining the e/m ratio and charge (e) of the electron, it is possible to calculate mass of the
electron.
Thomson experiment: e/m = 1.758 x 108 C/g
Millikan experiment : e = 1.6 x 10-19 C

e 1.6 x1019 C
Mass of the electron, m = = = 9.1 x 10-28g (9.1 x 10-31kg )
e/m 1.758x108 c / g

Thus electron is a fundamental particle of atom carrying one unit negative charge and having mass nearly
equal to 1/1837th of mass of an atom hydrogen.

Anode rays [ Canal rays]

Goldstain discovered the existence of a new
types of rays in the discharge tube. He used a
perforated cathode in the discharge tube. On applying
electric field at low pressure, he observed a new type
of rays behind the cathode. These rays are called
anode rays or canal rays.

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Properties of anode rays.
1. Unlike cathode rays, the positively charged particles depend upon the nature of the gas present in
the discharge tube. They are simply the positively charged gaseous ions.
2. The charge to mass ratio of the particles in the anode rays depends upon nature of the gas taken in
the discharge tube.
3. Some positively charged particles carry a multiple of the fundamental unit electrical charge.
4. They are deflected towards negatively charged plate in an electric field. They are also deflected in
a magnetic field.

Origin of cathode rays and anode rays

Under the influence of high potential difference, the gas in the discharge tube is ionized. The
negatively charged particles produced (electrons) move towards anode as cathode rays. On their way they
collide with the atoms of the gas producing more electrons and positively charged particles. The positive
ions move towards cathode in the form of anode rays.

Discovery of proton
The charge to mass ratio of particles in the anode rays depend upon the nature of the gas in the
discharge tube. The e/m ratio was maximum when hydrogen gas taken in the tube. This means that the
positive particles formed from hydrogen are the lightest. These lightest positively charged particles were
named as protons.
The charge to mass ratio for proton = 9.58 x 104 C/g
Charge of the proton = 1.6 x 10-19 C
Mass of the proton = 1.673 x 10-24 g (1.673 x 10-27 kg)
The proton is the fundamental particle of atom carrying one unit positive charge and having mass equal to
the mass of one hydrogen atom. [Mass of proton = 1837 times the mass of an electron.]

Discovery of neutron
Neutrons were discovered by James Chadwick in 1932. He bombarded a thin film of beryllium
with α-particles. Then he observed that highly penetrating rays consisting of neutral particles were
produced.
4Be + 2He → 6C
9 4 12
+ 0n1
These neutral particles were named neutrons.
The mass of neutrons = 1.675 x 10-27 kg
They are present in all atoms except hydrogen.

Name Discoverer Symbol Absolute Relative Mass(Kg) Mass(amu) [Link]

charge charge (amu)

Electron [Link] e -1.6 x 10-19 C -1 9.1 x 10-31 0.00054 0

Proton Goldstain p 1.6 x 10-19 C +1 1.673x 10-27 1.007 1

Neutron Chadwick n 0 0 1.675x10-27 1.008 1

EARLIER ATOMIC MODELS

1. Thomsons model of atom

[Link] in 1898 proposed the first atom model. He

proposed that an atom consists a uniform sphere of
positive electricity (radius= 10-10 m) in which electrons
are distributed more or less uniformly. In this model,
atom is visualized as a pudding or cake of positive charge
with raisins (electrons) embedded into it. Therefore this

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model is also called ‘plum pudding’ or ‘raisin pudding’
or ‘water melon’model.
The important feature of this model is that the mass of the atom is assumed to be uniformly
distributed over the atom.
This model could explain the electrical neutrality of atom. But it could not explain the results of
gold foil scattering experiment carried out by Rutherford.

Rutherford’s scattering experiment

Thomson’s atom model was tested by Rutherford in 1909 by his famous α-scattering experiment.
The experiment involved the bombardment of a thin sheet of gold (thickness = 100 nm) by α-particles.
Alpha particles are high energy positively charged helium nucleus emitted during radioactive decay. An
alpha particle has charge +2 and mass 4 u. The gold foil was surrounded by a circular fluorescent zinc
sulphide screen. Whenever an α-particle struck the screen, a tiny flash of light was produced at that point.

The important observations are

1. Most of the α-particles (about 99%) passed
through the gold foil un-deflected.
2. Some of these particles were deflected by small
angles.
3. A very few α-particles (one out of 20000) were
deflected back.

From these observations he made the following

conclusions.
1. Since most of the α-particles pass through the
foil un-deflected, it indicates that the most of the
space in an atom is empty.
2. The small angle of deflection of α-particles
indicates the presence of a heavy positive center
in the atom. Rutherford named the positive
center as nucleus.
3. Since the number of α-particles reflected back is
very small, it indicates that the space occupied
by the heavy positive center must be very small
The radius of the atom is about 10-10 m and that
of nucleus is about 10-15 m

[Link]’s atom model

On the basis of α-particle scattering experiment, Rutherford proposed the nuclear model of atom.
According to this model
1. An atom consists of a tiny positively charged nucleus at its center. The positive charge and most
of the mass of the atom is densely concentrated in the tiny nucleus.
2. The nucleus is surrounded by electrons. Electrons are moving around the nucleus with very high
speeds in circular paths called orbits.
3. The number of electrons in an atom is equal to the number of protons in it. Thus an atom is
electrically neutral.
4. Electrons and nucleus are held together by electrostatic force of attraction. The electrostatic force
of attraction is balanced by centrifugal force acting on the revolving electrons.

Nuclear model of atom resemble the solar system. The electron revolving around the nucleus is
just like the planets revolving around the sun. Therefore the electrons are called planetary electrons.

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Failure of Rutherford’s model

1. Rutherford’s model failed to explain the stability of atoms.

According to electromagnetic theory given by Maxwell, a charged
particle when accelerated emits energy in the form of
electromagnetic radiations. In Rutherford’s model, electrons are
revolving around the nucleus at high speeds. Therefore these
electrons would be in a state of acceleration all the time. Since
these electrons are charged particles they should emit radiation.
Hence their energy would decrease and they move closer and
closer to the nucleus and finally fall in the nucleus. But actually an
atom is stable. Thus Rutherford’s model cannot explain the
stability of atom.
2. Rutherford’s model also says nothing about the electronic structure of atoms.

Atomic number

The number of unit positive charges on the nucleus of an atom of the element is called atomic
number of the element. It is equal to the number of protons in the nucleus or the number of extra nuclear
electrons. It is denoted by the letter Z.
Atomic number (Z) = Number of protons
= Number of electrons

Mass number

Total number of protons and neutrons in the nucleus is called mass number of the atom. It is
denoted by the letter ‘A’
Mass number (A) = Number of protons + Number of neutrons
= Number of nucleons

Isotopes, Isobars and Isotones

Isotopes
Isotopes are the atoms of the same element with same atomic number but different mass number.
For example hydrogen has three isotopes, proteum (H), deuterium (D) and tritium (T).
They are represented as 1H1, 1H2 and 1H3.
All these have same atomic number (1), however their mass numbers are 1,2and 3 respectively.
The isotopes of oxygen are 8O16, 8O17 and 8O18

Isobars
Atoms of different elements which have same mass number are called isobars. For example 6C14
14
and 7N are isobars.

Isotones
Isotones may be defined as the atoms of different elements containing same number of neutrons.
For example 6C13 and 7N14 are isotones.

Nature of electromagnetic radiation

Wave nature of radiation [James Maxwell]

James Maxwell suggested that when electrically charged particle moves under acceleration,
alternating electrical and magnetic in fields are produced and transmitted. These fields are transmitted in

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the forms of waves called electromagnetic waves. The electromagnetic waves have the following
properties.
1. They are associated with oscillating electric
and magnetic fields, acting perpendicular to
each other and perpendicular to the direction
of their propagation.
2. In vacuum all electromagnetic waves travel
with the velocity of light (3 x108m/s).
3. These rays do not require any medium for
propagation and can move in vacuum.
4. There are many types of electromagnetic
radiations which differ from one another in
wavelength or frequency. The arrangement
of these waves in the increasing order of
wavelength is called the electromagnetic
spectrum.

In order to characterize these waves the following parameters are used

a). Wavelength

It is defined as the distance between two neighboring

crests or troughs of the wave. It is represented by Greek letter
‘λ’ (lambda). Its SI unit is meter(m). It is also measured in
Angstrom units (A0) or nanometers (nm).
1 A0 = 10-10 m 1nm = 10-9 m

b). Frequency

It is defined as the number of waves which pass through a particular point in one second. It is
represented by Greek letter ‘ν’ (nu). Its SI unit is Hertz (Hz) or Cycles per second (cps).
1 cps = 1 Hz 1kHz = 103 Hz
c). Velocity
The distance traveled by a wave in one second is called velocity of the wave. It is denoted by the
letter ‘c’
The frequency (ν) and wavelength (λ) are related to velocity ‘c’ by the relation

c =νλ or ν = c/λ
d). Wave number.
It may be defined as the number of wavelengths per unit length. It is equal to the inverse of the
wavelength. It is denoted by ‘ν’.
ν = 1/ λ = ν /c
It generally expressed as m-1 or cm-1

e). Amplitude
It is the height of a crest or depth of a trough of a wave. It is generally expressed by the letter ‘ a’.
The amplitude of the wave determines the intensity of radiation.

Electromagnetic spectrum

Arrangement of all the electromagnetic radiations in the increasing order of their wavelengths or
decreasing order of their frequencies is called electromagnetic spectrum.

Different regions of electromagnetic spectrum are known by different names. They have different
energies and are being used for different purposes. Some examples are:

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 1. Radio frequency region ( around 106 Hz) → Used for broadcasting.
2. Microwave region ( around 1010 Hz ) → Used for radar.
3. Infrared region (around 1013 Hz ) → It is the heat radiation
4. Ultraviolet region ( around 1016 Hz ) → A component of sun’s radiation.
5. Visible light (around 1015 Hz) → It is only part which our eyes can see or detect.

Limitation of wave theory of radiation

The wave theory was successful in explaining phenomena such as interference, diffraction etc. But
it failed to explain the following phenomena:
1. Black body radiation
2. Photoelectric effect
3. The variation of heat capacity of solids as a function of temperature.
4. Line spectra of atoms with special reference to hydrogen.

(a) Black body radiations:

The ideal body, which emits and absorbs radiations of all frequencies is called a black body. The
radiation emitted by such a body is called black body radiation.

When a black body is heated it becomes red hot. If

the temperature is further increased, the colour changes from
red to yellow to white and finally blue. This means that the
frequency of emitted radiation increases with increase in
temperature. [ Red colour → lower frequency, Blue colour
→ Higher frequency].

The intensity versus frequency of radiation from a

black body is given below. The frequency of emitted
radiation depends only on temperature. At a given
temperature, intensity increases with decrease of wavelength,
reaches a maximum and then starts decreasing
.
This observation could not be explained by wave
theory.

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(b) Photoelectric effect: [H. Hertz]
The phenomenon of ejection of electrons form the
surface of certain metals (eg; K, Rb, Cesium) when light of
suitable frequency strikes on it is called photoelectric effect.
The electrons ejected are called photoelectrons. The important
observations about photoelectric effect are:

(1) The electrons are ejected from the metal surface as

soon as the beam of light strikes the surface.
(2) Only light of certain minimum frequency can cause
the photoelectric effect from a particular metal. That
frequency is called threshold frequency (υo)
(3) The kinetic energy of the photoelectrons is directly proportional to the frequency of the incident
radiation, but is independent of its intensity.
(4) The number of photoelectrons emitted per second is directly proportional to the intensity of the
incident radiation.
These observations could not be explained by wave theory. According to wave theory light of any
frequency can be made to have sufficient, energy to cause emission of electrons by increasing its intensity.
Moreover the kinetic energy of ejected electron should be proportional to the intensity of light.

Particle nature of radiation [Plank’s quantum theory]

Particle nature of radiation is guided by the Plank’s quantum theory proposed by Max Plank. The
main points of the theory are,
1. The radiant energy is emitted or absorbed discontinuously in the form of small packets of energy
called quantum. In the case light these particles are called photons.
2. The energy of each quantum is directly proportional to the frequency of the radiation.

E∞υ or E=hυ or E = hc

Where ‘h’ is a constant called Plank’s constant. Its value is 6.626 x 10 -34 JS.
3. A body can emit or absorb energy only in terms of the integral multiples of quantum.
E = n hυ Where n = 1,2,3,----
Both black body radiation and photoelectric effect can be successfully explained by Plank’s theory.

(1) Explanation for Black body radiation:

When a black body is heated continuously, it undergoes a series of colour changes. This is because
when energy is supplied in the form of heat, it brings about change in its frequency (E ∞ υ ) . Since there is
a direct co-relation between colour and frequency, the colour change on heating can be justified.

(2) Explanation for photoelectric effect:

(a)Photoelectric effect can be explained on the basis of particle nature of light. According to it,
light is a stream of photons. Each photon is a source of energy (E =hυ ). The electrons are held to the metal
atom by certain force called binding energy. To overcome these forces certain minimum amount of energy
is required. This minimum energy is known as threshold energy or work function. [ E = hυo ] . Therefore
to cause ejection of electrons the photon of incident light should have energy equal to or greater than the
threshold energy (work function). If the energy of the incident photons are higher than the threshold
energy, the extra energy is taken up by the electrons that are ejected as kinetic energy.

Energy of incident photon (hυ) = Work function (hυo) + Kinetic Energy

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 hυ = hυo + 1
me v 2
2
1
me v 2 = hυ - hυ
o

2
= h (υ - υo )
= hc[ 1/λ – 1/ λ]
Thus for causing photoelectric effect, light of certain minimum frequency is required. Also
increasing the frequency of radiation increases the velocity (or kinetic energy ) of electrons.

(b) An intense beam of light consists of larger no of photons. Consequently the no electrons
ejected is also larger. Therefore the number of photoelectrons emitted per second is directly proportional to
the intensity of incident light.

Dual nature of radiation

Dual nature of radiation (light) was proposed by Einstein in 1905. Some characteristics of light
such as interference, diffraction etc are explained only by the wave nature. But some other properties like
black body radiation, photoelectric effect etc can be explained only by particle nature of light. So it can be
suggested that light can behave as particles as well as wave. Einstein even calculated the mass of a photon
associated with a radiation of frequency ‘υ’ as given below.

Energy E of the photon E = h υ ----- (1)

According to Einstein’s equation, E = mc2 ----- (2) where ‘m’ is the mass of photon.
From equations (1) and (2), we get
hυ = mc2
hc/λ = mc2
h
m
c
This equation can be used to calculate the mass of the photon.

Atomic spectrum

When a beam of light is passed through a prism, it splits up into seven colours (VIBGYOR). This
phenomenon of splitting of a beam of light into radiation of different frequencies by passing through a
prism is called dispersion. The pattern of radiation obtained after dispersion is called spectrum.

In the spectrum obtained from white light, the colours change from violet to red without any
discontinuity. This means that each colour merges into the other. Such a spectrum is called continuous
spectrum.

When an element is excited by heating, by passing electric discharge etc, the atoms of the element
emit electromagnetic radiations. The arrangement of these radiations in the increasing order of wavelength
is called emission spectrum of the element. Since these radiations are emitted due to energy changes taking
place in the atoms, it is also known as atomic spectrum.

The atomic spectra of the elements consist of bright lines separated by dark bands. That is they do
not show a continuous spread of wavelengths. Such spectrum is called line spectrum. The various lines in
the spectrum correspond to the radiations of different wavelengths.

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 The lines in the line spectrum of an element are characteristic of the atoms of the element.
Therefore the atomic spectrum of an element can be used to identify the element. Hence atomic spectrum is
sometimes called fingerprint of atoms.

Absorption spectrum

An absorption spectrum is obtained when a beam of continuous light is passed through vapours or
a solution of a substance and the transmitted light is analyzed in a spectroscope. The spectrum thus
obtained contains a number of dark lines. These dark lines appear due to the absorption of radiation of
corresponding wavelengths by the substance. The dark lines in the absorption spectrum of the substance
appear at the same position as the bright line in the emission spectrum of the substance.

Spectroscopy
The study of emission or absorption spectra is referred to as spectroscopy.

Hydrogen spectrum

When an electric discharge is passed through hydrogen gas in a discharge tube at low pressuure,
its molecules dissociate into hydrogen atoms. The excited hydrogen atoms emit electromagnetic radiations
of discrete frequencies. The emitted light is then analyzed with a spectroscope.
The spectrum of hydrogen thus obtained consists of several series of lines. These series of lines
are named after their discoverers. The lines of hydrogen spectrum are present in ultraviolet, visible and
infra-red regions.

The five different series of lines in the hydrogen spectrum are

1. Liman series - Ultraviolet region
2 Balmer series - Visible region
3. Paschen series
4. Brackett series Infra-red region
5. Pfund series.

Balmer showed that when the spectral lines are expressed in terms of wave number, the lines in the
visible region (Balmer series ) obey the formula


1 1
  109,677  2  cm-1 Where n = 3,4,5,…
2 n 
2

Then Rydberg gave a general formula which is applicable for all the series in the hydrogen spectrum
 1 1
  109,677 2
 2  cm-1
 n1 n2 

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Where n1 and n2 are integers.

For
Lyman series, n1 = 1 n2 = 2,3,4 ….
Balmer series n1 = 2 n2 = 3,4,5….
Paschen series n1 = 3 n2 = 4,5,6 ….
Brackett series n1 = 4 n2 = 5,6,7 ….
Pfund series n1 = 5 n2 = 6,7,8 ….

Bohr model of atom

Niels Bohr in 1913 proposed his atom model. The main points of this model are
1. The electrons in atom are revolving around the nucleus only in certain selected circular orbits.
These orbits are associated with definite energies and are called energy shells or energy levels. These
are numbered as 1,2,3,4 etc and are designated as K,L,M,N……

2. The energy of an electron in an orbit does not change

with time. This means that energy of an electron in a
particular orbit remains constant. That is why these
orbits are also called stationary orbits.

3. The electron can move only in those orbit for which its
angular momentum is an integral multiple of h/2π
(where h is the Planck’s constant)
Angular momentum of the electron,
mvr = nh/2π where n = 1,2,3….
In other words, angular momentum of electrons in an
atom is quantised. This indicates that only certain fixed
orbits are allowed.
4. When energy is supplied to the electron, it may jump from lower energy level to higher energy
level by absorbing a definite amount of energy. When the electron jumps back to the lower energy
level, it radiates same amount of energy in the form of photons of radiation.

ΔE = E2 –E1 = hυ
υ = E2 –E1
h
This expression is commonly known as Bohr’s frequency rule

Success of Bohr’s model

1) Bohr’s model could explain the stability of an atom.

According to Bohr’s model an electron will lose energy only when it jumps from higher energy
level to lower energy level. If no lower energy level is vacant, it will remain in the same orbit without
losing energy. Hence it explain the stability of atom.

2) Bohr’s theory helped in calculating the energy of an electron in a particular orbit of hydrogen.
The energy of an electron in the n th orbit of hydrogen is given by
 1 
En   RH  2  n = 1,2,3,…..
n 
where RH is called Rydberg constant and its value is 2.18 X 10-18 J
2.18  1018
En   J/atom
n2

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3) Radius of orbits
Bohr also calculated the radius of circular orbits in hydrogen atoms. The radius can be given by
the expression
rn = n2 x 52.9 pm Where n = 1,2,3-----

The radius of first orbit of hydrogen is equal to 52.9 pm. This is also known as Bohr radius. As ‘n’
increases the radius of the orbit increases.

4) Bohr model is also applicable to ions such as He +, Li2+ etc which like hydrogen atom contain one
electron. For them the equation for energy and radius are

 2.178x1018 Z 2 J/atom
En 
n2

rn = n2(52.9) pm
Z
Where Z is the atomic number [ For He+, Z = 2 and for Li2+ Z = 3]

5) It is also possible to calculate the velocity of electrons in the orbits. The velocity increases with nuclear
charge but decreases with principal quantum number.

6) Bohr’s model could explain the atomic spectrum of hydrogen.

According to Bohr model electron can have only certain definite energy levels. When energy is
absorbed by the atom, electron moves from a lower energy orbit to a higher energy orbit. Conversely when
energy (radiation) is emitted, electron moves from a higher energy orbit to a lower energy orbit.

Suppose an electron in an excited state with n = n2 drops to a lower energy state with n = n 1. The
difference in energies between two states is given by

E  En2  En1

  2.18x1018 j    2.18x1018 j 
E    
 n22   n12 

1 1
= 2.18x1018  2  2  J
 n1 n2 

E = hυ

hυ = 1 1
2.18x1018  2  2  J
 1
n n2 

h = 6.626x10-34 JS

υ 2.18x1018  1 1  -1
Therefore =
-34  2
 2 S
6.626 x 10  n1 n2 

  2.18x1018 1 1
In terms of wave number  = =  2 m
-1
8  2
c -34
6.626 x 10 x3x10  n1 n2 

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 = 1 1  -1
1.09677x107  2  2  m
 n1 n2 
The above equation is same as the Rhydberg equation deduced from experimental data.

Bohr’s model also accounts for the existence of

large number of lines in hydrogen spectrum. In the
case of large number of hydrogen atoms, different
transitions are possible. This leads to large number
of spectral lines.

The transitions of electrons from higher

energy levels to the first energy level are grouped
together as Lyman series. The transitions of
electrons from higher energy levels to the second
energy level are grouped together as Balmer series.
Similarly transitions to the 3rd , 4th and 5th energy
levels give rise to Paschen, Brackett and Pfund
series respectively.

Negative value of electronic energy

When an electron is at infinite distance from the nucleus, there is no force of attraction between
the electron and the nucleus. The energy of such an electron is arbitrarily assumed to be zero. When the
electron moves towards the nucleus, energy released due to force of attraction. Therefore the energy of
electron becomes less than zero. That is why energy of electron is negative.

Shortcomings of Bohr’s model

Bohr’s model has the following limitations.

1. Bohr’s model could not explain the spectra of atoms containing more than one electron.
2. The model failed to explain the fine structure of hydrogen spectrum. By using spectroscopes of
high resolving power, it is observed that each line of hydrogen spectrum splits in to two closely
spaced lines. This is known as the fine spectrum.
3. It is observed that in the presence of a magnetic field, each spectral line gets split up into closely
spaced lines. This phenomenon is known as Zeeman effect. Similarly the splitting of spectral lines
under an electric field is called Stark effect. These effects could not be explained by Bohr’s
model.
4. It could not explain the ability of atoms to form molecules by chemical bonds.
5. de Broglie suggested that electron like light, has a dual character. (particle and wave character).
But Bohr had treated electron only as a particle.
6. Bohr model is contrary to Heisenberg’s uncertainty principle.

Dual nature of matter – de Broglie Equation.

Louis de Broglie in 1924 postulated that matter, like radiation, should exhibit a dual behaviour ie
wave and particle nature. He derived a relationship between the wavelength (λ) of a material particle, its
linear momentum (p) and planks constant (h)

h h
λ = =
mv p

The waves associated with particle in motion are called matter waves or de Broglie waves.

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Derivation for de Broglie Equation
de Broglie Equation has been derived initially for photons of light based on Planck’s quantum
theory and Einstein’s equation.
According to Planck’s theory,

Energy of a photon, E = hυ where ‘υ’ is the frequency of light.

According to Einsteine’s equation,
Energy, E = mc2
Comparing the above two equations,
hυ = mc2
hc
= mc2

hc h
λ = 2
=
mc mc
For a particle having mass ‘m’ and velocity ‘v’
h
λ =
mv

The above equation implies that heavier particles have shorter wavelength than lighter particles.
Similarly the wavelength of a particle decreases as its velocity increases.

de Broglie’s prediction was confirmed experimentally when it was found that an electron beam
undergoes diffraction. Diffraction is a phenomenon characteristic of waves. This principle is used in
electron microscope. Electron microscope is based on the wave like behaviour of electrons.

de Broglie equation can be applied only to the moving microscopic particles like electron, proton,
atoms etc. It has no relevance for the moving macroscopic particles. This is because for macroscopic
particles such as a bullet or a ball, the de Broglie wavelength is so small and it cannot be measured.

Heisenberg uncertainty principle

Heisenberg uncertainty principle states that it is impossible to determine simultaneously both the
position and momentum of a microscopic particle like electron with accuracy or certainty.

Mathematically, Δx. Δp ≥ h/4π

Where Δx is the uncertainty in position and Δp is the uncertainty in momentum.

But p = mv
Ie Δp = mΔv
Therefore the above relation is Δx (m Δv) ≥ h/4 π

Or Δx . Δv ≥ h/4πm
Ie the position and velocity of a microscopic particle cannot be determined with certainty.

Significance of uncertainty principle

1. Heisenberg uncertainty principle rules out the existence of definite paths or trajectories for an
electron. The position and velocity of an object fix its trajectory or path. If it is not possible to
determine accurately the position and velocity of a particle at any given instant, it is not possible
to fix its trajectory. Hence the uncertainty principle replaced the concept of definite orbits by the
concept of probability (orbitals).

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 2. The effect of Heisenberg uncertainty principle is significant only for microscopic objects and is
negligible for macroscopic objects.
Reasons for the failure of the Bohr Model
In Bohr model electron is defined as a charged particle moving in a well defined circular orbit.
But according to de Broglie concept electron has duel character [wave and particle nature]. The wave
character of electron is not considered in Bohr model. Moreover the orbit in Bohr model is a clearly defined
path. But this path can be completely defined only if both position and velocity of electron are known at the
same time. This is against Heisenberg’s uncertainty principle.

Quantum mechanics
On the basis dual nature of matter and Hesenberg’s uncertainty principle, Erwin Schrodinger
developed a new branch of science called Quantum mechanics. Schrodinger developed an atomic model
taking into account both the wave and particle nature of the electron. This is known as wave mechanical
model of atom.

Important features of quantum mechanical model of atom:

The important features of quantum mechanical model of atom are
1) The energy of electrons in atoms is quantized.(It can have only certain specific values.)
2) The existence of quantized electronic energy levels is a direct result of the wave like properties of
electrons.
3) Both the exact position and velocity of an electron in an atom cannot be determined
simultaneously.
4) The atomic orbital is the wave function ψ for an electron in atom. Since many wave functions are
possible for an electron, there are many atomic orbitals in an atom. In each orbital the electron has
a definite energy. An orbital cannot contain more than two electrons. Electrons are filled in these
orbitals in the order of increasing energy.
5) The probability of finding an electron at a point within an atom is proportional to the square of the
orbital wave function ψ2 at that point.

Physical significance of ψ and ψ2

Ψ refers to the amplitude of the electron wave. It has no physical significance. However ψ 2 is very
important. ψ2 gives the intensity of electron in the space around the nucleus of the atom. In other words ψ 2
gives the probability of finding an electron in a particular region around the nucleus. Thus ψ2 is called
probability density and ψ is called probability amplitude.

Orbit and Orbital:

An orbit, as proposed by Bohr is a circular path around the nucleus in which an electron moves.

An orbital on the other hand is a quantum mechanical concept An orbital may be defined as the
regional space around the nucleus where the probability of finding an electron is the maximum (90 to
95%).

The important differences between orbit and an orbital are:

Orbit Orbital
1. It is a well defined circular path 1. It is the region around the nucleus where the
around the nucleus probability of finding an electron is the
maximum.
2. Orbits are circular in shape 2. Orbital have different shapes. Eg: s-orbital is
spherical and p-orbital is dumb-bell shaped.
3. The maximum number of electrons 3. An orbital cannot accommodate more than
in an orbit is given by 2n 2 two electrons.
4. Orbits are non directional in 4. Orbitals (except s-orbital) have directional
character. character.

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Quantum Numbers:

Each atomic orbital in an atom, is designated by a set of three numbers known as quantum
numbers. These quantum numbers specify, size, shape and orientation of the electron orbital. These are
principal quantum number (n), azimuthal quantum number (l) and magnetic quantum number (ml). These
follow directly from solution of Shrodinger wave equation. In order to designate an electron an additional
quantum number called spin quantum number is also needed (spin quantum number). It specifies the spin
of the electrons.

(1) The Principal quantum number (n)

It is the most important quantum number since it tells the principal energy level or shell to which
an electron belongs. It also gives the average distance of the electron from the nucleus. Thus it determines
the size of the orbital. It is denoted by the letter, ‘n’. It can have any integral values except zero ie n=
1,2,3,4,----. The principal energy levels are also designated by the letters K, L, M, N etc. Higher the value
of ‘n’ the higher is the electronic energy. There are n2 orbitals in a shell. The maximum number of
electrons in a shell is given by 2n2.

(2) The angular momentum quantum number or Azimuthal quantum number (l) or Subsidiary quantum number:

This quantum number is related to the orbital angular momentum of the electron. This is denoted
by l. The orbital angular momentum of the electron is given by

Orbital angular momentum = h √l(l+1)

2π
The value of ‘l’ gives the sub level or sub-shell in which the electron is located. It determines the
shape of the orbital. It can have all possible whole number values from 0 to n-1. The various sub-shells are
designated as s, p, d, f. depending upon the value of ‘l’.

Value of ‘l’ 0 1 2 3 4
Designation of sub-shell s p d f g

When n=1, ‘l’ can have only one value. ie ‘0’. It means that the first energy level has only one sub-
shell (s- sub-shell)
When n = 2, ‘l’ can have two values, 0 and 1. It means that the second principal energy level has two
sub-shells. [s-sub-shell (2s) and p-sub-shell(2p)]
When n = 3, ‘l’ can have three values, 0, 1 and 2. It means that the third principal energy level has
three sub-shells. [s-sub-shell (3s), p-sub-shell (3p) and d-sub-shell (3d)]

(3) The magnetic quantum number (m l) :

Magnetic quantum number specifies the different orientations of electron cloud in a particular sub-
shell. The different orientations are called orbitals. It is denoted by ml. For a given value of ‘l’, it can have
all integral values from –l to +l through zero. Thus it makes a total of (2l+1) values.
For l= 0(s-sub-shell), ml can have only one value ml = 0. If means that s-sub-shell has only one orbital.
For l=1( p sub-shell) ml can have 3 values –1, 0, +1. This implies that p-sub-shell has 3 orbitals.
For l=2(d-sub-shell) ml can have the values –2,-1,0,+1,+2. Thus for d-sub-shell there are five orbitals.

(4) The spin Quantum number(s):

The electron moving around the nucleus also rotates or spin about its own axis. Therefore it has
spin angular momentum. Spin angular momentum of the electron is a vector quantity and can have two
orientations relative to the chosen axis. These two orientations are distinguished by the spin quantum
numbers ‘ms’. The spin quantum number can have only two values that are +1/2 and –1/2. The +1/2 value
indicates clockwise spin (↑) and –1/2 indicates anticlockwise spin (↓). This implies that an orbital can hold
only two electrons and these electrons should have opposite spins.

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Shapes of atomic orbitals

The variation of ψ and ψ2 as a function of r

for 1s and 2s electron is shown in fig.

For 1s orbital the probability density is

maximum at the nucleus and it decreases sharply as the
distance increases. But for 2s orbital the probability
density first decreases sharply to zero and starts
increasing. After approaching a small maximum it
again decreases. The region where the probability
reduces to zero is called nodal surface or simply node
[radial node].
In general ns orbital has (n-1) nodes.
Eg. Number of nodes for 2s orbital = 1
Number of nodes for 3s orbital = 2

The shapes of orbitals or the representation of the variation of ψ2 in space can be given by two
approaches.
(1)Charge cloud diagrams and (2) Boundary surface diagrams.

[Link] cloud diagrams:

Here the probability density ψ2 is shown as a collection of dots. The density of dots in any region
represents the electron probability density in that region.
Charge cloud diagrams of 1s and 2s orbitals is given below.

[Link] surface diagrams

In boundary surface diagrams, the shape of an orbital

is defined as a surface of constant probability density that
encloses some large fraction (90%) of the probability of
finding the electron

According to this model an s-orbital has the shape of

a spherical shell centered on the nucleus. As the value of ‘n’
increases the size of the spherical shell increases.

Boundary surface diagrams of p-orbitals are shown in fig. Each p-orbital is dumb-bell shaped. For
p-orbitals there are 3 possible orientations of electron cloud. They are designated as p x, py and pz. Of these
px orbital is oriented along x-axis and, py and pz are oriented along y-axis and z-axis respectively. Each p-
orbital consists of two sections called lobes. These lobes are on either side of the plane that passes through
the nucleus. Thus the two lobes are separated by a plane of zero probability called nodal plane. For px
orbital the nodal plane is YZ and for py and pz, the nodal planes are ZX and XY respectively.

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 Boundary surface diagrams of d-orbitals are shown in fig. There are five d-orbitals. These are
designated as dxy, dyz, dxz, dx2-y2 and dz2. All the five 3d-orbitals are equivalent in energy.

Angular nodes
Besides the radial nodes, p and d atomic orbitals have zero probability planes passing through the
origin (nucleus). For example in case of pz orbital, XY plane is the nodal plane. For a d orbital there are
two nodal planes passing through the origin. These are called angular nodes. The total number of angular
nodes for an orbital is given by ‘l’.

For an orbital
Total number of radial nodes = n-l-1
Total number of angular nodes = l
Total number of nodes = n-1

Electronic configuration of elements:

The distribution of electrons of an atom in its various orbitals is called its electronic configuration.
It is goverened by the following rules.

(1) Aufbau principle:

According to this rule, electrons in an atom are filled in orbitals in order of their increasing energies.
The order of increase of energy of orbitals can be calculated from the (n+l) rule. ( Bohr’s Bury’s rule).
According to this rule
1. The orbital having lower (n+l) value has lower
energy.
For example:
For 4 s orbital; n+l = 4 + 0 = 4
For 3 d orbital; n+l = 3 + 2 = 5
Since 4s orbital has lower (n + l) value, it will fill
before 3d.
2. If two orbitals have the same (n+l) value, the one
with lower ‘n’ will be filled first.
For example:
For 2 p orbital; n+l = 2 + 1 = 3
For 3 s orbital; n+l = 3 + 0 = 3
Since 2p-orbital has lower value of ‘n’ it has
lower energy than 3s and it will be filled first.

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The order in which the energies of orbitals increase is as follows. Therefore they also fill in the same order.
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p

2) Pauli’s exclusion principle

This principle states that no two electrons in an atom can have the same set of four quantum
numbers. It follows that an orbital can accommodate two electrons and these electrons must have opposite
spins.

3) Hund’s rule of maximum multiplicity

This rule states that pairing of electrons in the orbitals of same subshell does not take place until
all the orbitals of the sub-shell are singly occupied. Moreover the singly occupied orbitals must have the
electrons with parallel spins.

Degenerate orbitals
The orbitals having same energy are called degenerate orbitals. Eg. 2px, 2py and 2pz orbitals are
having same energy and therefore they are degenerate orbitals.

Representation of electronic configuration

The electronic configuration of an atom is written by filling of atomic orbitals in the increasing
order of their energies. This can be done in two ways.

1. Orbital notation method.

For example the electronic configuration of neon (10Ne)is written as 1s2 2s2 2p6.
The only draw back of this method is that one cannot get any idea about the spins of individual electrons
from the notations.

2. Orbital diagram method.

Here the orbitals are represented as boxes and the electrons by arrows. The spins of the electrons
are represented by the direction of these arrows.
Some more examples are:

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