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UNIT 1
ATOMIC STRUCTURE
Dalton, in 1808 proposed that matter was made up of
extremely small, invisible particles called atoms (Greek, atom
means cannot be cut).
Matter: Anything that occupies space and has mass is called
matter.
Atom
An atom is the defining structure of an element which
cannot be broken by any means. A typical atom consists of a
protons and neutrons with electrons orbiting this nucleus.

An atom is supposed to be made up of several particles.
Some of the particles are electrons, protons, neutrons, anti-
protons, positrons, neutrino, photons and gravitons etc., Among
these particles electrons, protons and neutrons are regarded as
the fundamental particles.
The charge and mass of these fundamental particles are
given below,
Particle Charge Mass (in amu)
Electron -1 (negative) 0.000548596
Proton +1 (positive) 1.00727663
Neutron 0 (neutral) 1.0086654

Nucleons
The nucleus of an atom consists of protons and
neutrons. The total number of neutrons and protons are known
as nucleons.
Example: Helium nucleus contains 2 protons and 2
neutrons (2He
4
)
The total number of nucleons in helium nucleus = 4
Nuclides
An atom which is specified by its symbol, atomic
number, atomic mass and charge is referred to as a nuclide.
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Atomic number (Z)
The number of protons in an element is called its atomic
number.
Mass number (A)
The total number of protons and neutrons in a nucleus
of an element is called its mass number.
A = Z + N
where, N is the number of protons in the nucleus of an element
N = A Z
Rutherfords Atom model
In 1911, Rutherford bombarded a stream of highly
energetic -particles from a radioactive source against a thin
gold foil.
After passing through the metal sheet the -particles are
made to struck a zinc sulphide screen.

Based on these observations, Rutherford proposed a
model of atom. According to his theory,
1. Atom has a tiny dense core or the nucleus which
contains the entire mass of the atom, leaving the rest of
the atom almost empty.
2. The entire positive charge of the atom is located on the
nucleus while electrons were distributed in vacant
space around it.
3. The electrons were moving in orbits or closed circular
paths around the nucleus like planets around the sun.


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Drawbacks of Rutherford atom model
1. It could not explain how the electrons and protons could
be close packed to give a stable nucleus.
2. If a charged particle accelerates around an oppositely
charged particle, it will radiate energy. If an electron
radiates energy its speed will decrease and finally
falling into the nucleus and the atom would be unstable.
But really atom is stable.
Bohrs Atom model
In 1913,NeilsBohr successfully developed model for
hydrogen atom on the basis of quantum theory.
Postulates:
1. Bohr considered the atom consists of a positively
charged nucleus with electrons revolving around it
without emitting any energy.
2. Electrons can move around the nucleus only in certain
definite orbits, whose angular momentum (mur) is an
integral multiple of the factor h/2.
i.e.,
t 2
h
n mur =

where, m = mass of the electron
u = velocity of the electron
r = radius of the orbit
h = Plancks constant (6.626 x 10
-34
Kg.m
2
.S
-1
)
n = number of orbit in which electron is present.
3. Electrons in each orbit have a definite energy and are
at a fixed distance from the nucleus. The orbits are
designated as K, L, M, N etc., (or) 1,2,3,4 etc., (from nucleus
to outwards)
4. In these specific orbits, an electron does not radiate
energy. Therefore in each of these orbits, the energy of
an electron remains the same. Hence an orbit is called
stationary energy level or energy level.
5. An electron can move from one energy level to another
by absorbing or emitting quantum of energy.
6. An electron in its lowest energy state is said to be in the
ground state, whereas an electron in its higher energy
state is said to be in the excited state. The ground state
is the most stable state of the atom.
7. The quantum of energy absorbed or emitted is equal to
the energy difference between the lower and higher
energy levels of the atom.
v h E E E = = A
1 2

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where, E1 and E2 are the energies of the electron in the
first and second energy levels.
h = Plancks constant (6.626 x 10
-34
Kg.m
2
.S
-1
)
= frequency of photon
Bohrs Theory of Hydrogen Spectrum
Bohr proposed a theory to explain the emission of line
spectra from hydrogen atom.
1) Let us consider a hydrogen atom in the ground state.
The electron is in the first or K-shell.
2) If the electron absorbs energy (radiation), the electron
moves into a higher energy level (n= 2,3, ) depending
upon the energy absorbed by it.

3) The electron is in an excited state now. This is an
unstable situation. The electron therefore falls back
immediately to one of the lower levels or even to the
ground state.
4) The difference in energy possessed by the electron in the
higher level and the lower level is emitted in the form of
line spectrum.
5) Let us consider the energy of the higher energy level be
E2 and that of the lower energy level be E1. Then,
h
E E c
h
E E
h E E
1
2
1
2
1 2

=
=

v
v

6) Hydrogen atom contains only one electron. But its
spectrum consists of a large number of lines. The reason
is,
A sample of hydrogen contains a very large number of
atoms. When energy is supplied to the sample of the
hydrogen gas, different atoms absorb different amount
of energies.
So, electrons in different atoms will move up to
different energy levels depending upon the energy
absorbed by the atoms.
When electrons fall back, they fall from different energy
levels and reach different energy levels. Hence we get
several spectral lines with varied wave lengths. Hence
we get several spectral lines with varied wave lengths.
If n is the frequency of the line emitted, then,
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(
(

=
2
2
2
1
3 2
0
4 2
1 1
) 4 (
2
n n h
me
tc
t
v

where,
0
is a constant
m is the mass of the electron
e is the charge of the electron
n1 is the lower energy level
n2 is the higher energy level
(
(

= =
(
(

=
(
(

=
2
2
2
1
2
2
2
1
3 2
0
4 2
2
2
2
1
3 2
0
4 2
1 1 1
1 1
) 4 (
2 1
1 1
) 4 (
2
n n
R
n n c h
me
n n h
me c
H

v
tc
t

tc
t


where, RH is called the Rydberg constant of the
hydrogen atom.
3 2
0
4 2
) 4 (
2
h
me
R
H
tc
t
=

Depending on the values of n1 and n2 we get various
series of spectral lines.

Name of the series n1 n2
Lyman 1 2,3, .
Balmer 2 3,4, .
Paschen 3 4,5, .
Bracket 4 5,6, .
Pfund 5 6,7, .

Successes of Bohrs Theory
1) Bohrs theory of hydrogen atom enabled the
calculation of radii and energies of orbits in
hydrogen atom.
2) It explained successfully the positions of various
series of lines in the hydrogen atom.
Limitations of Bohrs Theory
1) It explains the spectrum of species having only one
electron, i.e., hydrogen atom, He
+
, Li
2+
, Be
3+
, etc., It does
not explain the spectra of atoms having more than
one electron.
2) When the spectrum of hydrogen was taken with
modern spectroscopes, the line spectra of hydrogen
shows the presence of fine structure, i.e., each line in
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the original spectrum was found to consist of a
group of very fine lines.
Sommerfelds Atom Model
In order to account for the fine structure of spectral
lines, Sommerfeld modified Bohrs theory. According to
Sommerfeld,
1. Electrons are revolving around the nucleus in elliptical
orbits like the planets around the sun.
2. An ellipse has two axes
(i) Major axis
(ii) Minor axis
3. As the orbit broadens, the length of the two axes become
closer and they become equal when the orbit becomes
circular.

4. It can be shown that, n the principal quantum number
used by Bohr and K the azimuthal quantum number
used by Sommerfeld are related to one another as,
axis or of length
axis major of length
K
n
min
=

5. K can have values from 1 to n. when n = 3, there are three
values of K equal to 1,2 and 3. Therefore there will be
three Sommerfeld orbits (one circular and two
elliptical).
Drawbacks of Sommerfeld atomic model
1. The modern wave mechanics shows that the
azimuthal quantum number can have values from 0
to n-1 and not from 1 to n as proposed by
Sommerfelds theory.
2. It does not explain the Zeeman effect and Stark
effect.
3. It fails to provide accurate values for the angular
momentum of electrons which move in elliptical
orbits.
de-Broglies Theory
1. In Bohrs theory electron is treated as a material
particle of small mass moving round the nucleus in
a fixed path ( i.e., orbit ).
2. Light which consists of electromagnetic radiations is
known to exhibit both particle and wave properties.
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3. Based on the analogy, a French Physicist Louis de-
Broglie (1923) suggested that:
4. Matter, considered to be made up of discrete
particles such as atoms and molecules, may also
behave like wave under proper condition.
5. This leads to the view that electrons like the light
may also have wave properties associated with
them. It means that an electron has a dual nature
i.e., particle and wave.
de-Broglies Equation
According to de-Broglie, an electron of mass m moving
with velocity u should be associated with a wave having wave
length .
It can be represented as,

___________ 1
where, h is the Plancks constant
mu is the momentum of the moving particle.
Equation 1 can be written as,


or

___________ 2
Equation 2 is the form of de-Broglie relationship and this can be
stated in words as;
The momentum of a moving particle is inversely
proportional to the wavelength of the waves associated with it.
Derivation
According to Plancks quantum theory, the energy of a
photon is equal to
i.e., ___________ 1
We know that,

___________ 2
According to Einsteins mass energy relationship,

___________ 3
Compare Eqn. 2 and 3, we have,


or


or

___________ 4
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where, p is the momentum of the wave.
Eqn. 4 is the fundamental de-Broglies equation. This gives the
wavelength , of the matter wave associated with material
particles.
We can write Eqn. 4 as,

___________ 5
Application of de-Broglie concept
The main applications are:
1. The development of electron microscope is an
application of de-Broglies concept.
2. The de-Broglies concept has theoretically supported
Bohrs second postulate.
Heisenbergs Uncertainty Principle
Heisenberg states that, it is not possible to determine
precisely both the position and the momentum (velocity) of a
small moving particle.
It may be expressed as,

___________ 1
where, x = uncertainty in position
P = uncertainty in momentum
h = Plancks constant.
Eqn. 1 is known as Heisenbergs equation which can be stated in
words as, the product of uncertainty in the simultaneous
determination of the position and momentum of a particle is
equal or greater than the Plancks constant.
Since the minimum product of x and P is constant, it
means that,


It follows, if uncertainty in position (x) is less,
uncertainty in momentum (P) would be large.
Similarly, if uncertainty in momentum (P) is less,
uncertainty in position (x) would be large.