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ATOM
Thomson atom model
From the study of discharge of electricity through gases, it became clear that an atom
consists of positive and negative charges. J.J. Thomson tried to explain the arrangement of
positive charge and the electrons inside the atom.
According to him, an atom is a sphere of positive charge having a radius of the order of
10-10m. The positive charge is uniformly distributed over the entire sphere and the
electrons are embedded in the sphere of positive charge .
The total positive charge inside the atom is equal to the total negative charge carried by
the electrons, so that every atom is electrically neutral.
According to Thomson, if there is a single electron in the atom (like a hydrogen atom), the
electron must be situated at the centre of the positive sphere.
For an atom with two electrons (helium atom), the electrons should be situated
symmetrically with respect to the centre of the sphere i.e., opposite sides of the centre at
a distance of r/2 where r is the radius of the positive sphere. In a three electron system of
the atom, the electrons should be at the corners of a symmetrically placed equilateral
triangle, the side of which was equal to the radius of the sphere. In general, the electrons
of an atom are located in a symmetrical pattern with respect to the centre of the sphere.
It was suggested that spectral radiations are due to the simple harmonic motion of these
electrons on both sides of their mean positions. Moreover, the stability of the atom was
very well explained on the basis of this model
Drawbacks
(i) According to electromagnetic theory, the vibrating electron should radiate energy and
the frequency of the emitted spectral line should be the same as the electron. In the case
of hydrogen atom,
Thomson’s model gives only one spectral line of about 1300 Å. But the experimental
observations reveal that hydrogen spectrum consists of five different series with several
lines in each series.
(ii) It could not account for the scattering of α-particles through large angles.

Rutherford’s α - particle scattering experiment

Rutherford and his associates studied the scattering of the α - particles by a thin gold foil
in order to investigate the structure of the atom. An α-particle is a positively charged
particle having a mass equal to that of helium atom and positive charge in magnitude
equal to twice the charge of an electron. They are emitted by many radioactive elements.
The scattering of α-particles provide useful information about the structure of the atom.

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Experimental arrangement
214
A fine stream of α−particles was obtained from a radioactive material 𝐵𝑖83 by placing it in
a lead box with narrow opening as shown in Fig

The α-particles of energy 5.5MeV emitted from the source in all possible directions, but
only a narrow beam emerges from the lead box. The remaining α-particles are absorbed in
the lead box itself. After passing through the diaphragms D1 and D2, a narrow beam of α-
particles incident on a thin gold foil of thickness 2.1×10-7 m, are scattered through
different angles.
The scattered α-particles strike a fluorescent screen coated with zinc sulphide. When the
α-particles strike the screen, tiny flashes of light are produced.
The observations can be made with the help of a low power microscope.

Observations and conclusions

(i) Most of the α particles either passed straight through the gold foil or were scattered by
only small angles of the order of a few degrees.
This observation led to the conclusion that an atom has a lot of empty space.
(ii) A few α particles were scattered in the backward direction, which led Rutherford to
conclude that the whole of the positive charge was concentrated in a tiny space of about
10-14 m. This region of the atom was named as nucleus. Only a small number of particles
approaches the nucleus of the atom and they were deflected at large angles.

Distance of closest approach

An α particle directed towards the centre of the nucleus will move close up to a distance ro
as shown in Fig, where its kinetic energy will appear as electrostatic potential energy.
After this, the α particle begins to retrace its path. This distance ro is known as the distance
of the closest approach.
Let m and v be the mass and velocity of the α particle directed towards the centre of the
nucleus. Then, the kinetic energy of the particle,
1
𝐸𝑘 = 𝑚𝑣 2
2

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Since, charge of an α-particle is 2e and that of the nucleus of the atom is Ze, the
electrostatic potential energy of the α particle, when at a distance ro from the centre of
the nucleus is given by,
1 (2𝑒)(𝑍𝑒)
𝐸𝑃 =
4𝜋𝜀0 𝑟0
where Z is the atomic number of the atom and εo, the permittivity of free space.
On reaching the distance of the closest approach ro, the kinetic energy of the α particle
appears as its potential energy.
𝐸𝑝 = 𝐸𝑘
1 1 (2𝑒)(𝑍𝑒)
𝑚𝑣 2 =
2 4𝜋𝜀0 𝑟0
1 4𝑍𝑒 2
𝑟0 =
4𝜋𝜀0 𝑚𝑣 2
Drawbacks
Rutherford atom model offered serious difficulties as regards the stability of the atom.
Following are the two drawbacks of Rutherford’s model:
(i)The electron in the circular orbit experiences a centripetal acceleration. According to
electromagnetic theory, an accelerated electric charge must radiate energy in the form of
electromagnetic waves.
Therefore, if the accelerated electron loses energy by radiation, the energy of the electron
continuously decreases and it must spiral down into the nucleus. Thus, the atom cannot be
stable. But, it is well known that most of the atoms are stable.
(ii) According to classical electromagnetic theory, the accelerating electron must radiate
energy at a frequency proportional to the angular velocity of the electron. Therefore, as
the electron spiral towards the nucleus, the angular velocity tends to become infinity and
hence the frequency of the emitted energy will tend to infinity.
This will result in a continuous spectrum with all possible wavelengths. But experiments
reveal only line spectra of fixed wavelength from atoms.

Bohr atom model

Neils Bohr in 1913, modified Rutherford’s atom model in order to explain the stability of
the atom and the emission of sharp spectral lines. He proposed the following postulates:

(i) An electron cannot revolve round the nucleus in all possible orbits. The electrons can
revolve round the nucleus only in those allowed or permissible orbits for which the
angular momentum of the electron is an integral multiple of h/2π
(where h is Planck’s constant = 6.626 × 10-34 Js).
These orbits are called stationary orbits or non-radiating orbits and an electron revolving
in these orbits does not radiate any energy.
If m and v are the mass and velocity of the electron in a permitted orbit of radius r then
angular momentum of electron = mvr = nh/2π ,

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where n is called principal quantum number and has the integral values 1,2,3 … This is
called Bohr’s quantization condition.
(ii) An atom radiates energy, only when an electron jumps from a stationary orbit of higher
energy to an orbit of lower energy. If the electron jumps from an orbit of energy E2 to an
orbit of energy E1, a photon of energy hν = E2 – E1 is emitted. This condition is called Bohr’s
frequency condition.

Orbital velocity of electrons

Consider an atom whose nucleus has a positive charge Ze, where Z is the atomic number
that gives the number of protons in the nucleus and e, the charge of the electron which is
numerically equal to that of proton. Let an electron revolve around the nucleus in the nth
orbit of radius rn.
By Coulomb’s law, the electrostatic force of attraction between the nucleus and the
electron
1 (𝑍𝑒)(𝑒)
𝐹𝑒 =
4𝜋𝜀0 𝑟𝑛2
Since, the electron revolves in a circular orbit, it experiences a centripetal force
𝑚𝑣𝑛2
𝑟𝑛
The necessary centripetal force is provided by the electrostatic force of attraction
For equilibrium, from equations
1 (𝑍𝑒)(𝑒) 𝑚𝑣𝑛2
=
4𝜋𝜀0 𝑟𝑛2 𝑟𝑛

1 (𝑍𝑒)(𝑒)
𝑣𝑛2 =
4𝜋𝜀0 𝑟𝑛 𝑚

1 𝑍𝑒2
𝑣𝑛 = √ − − − 𝑒𝑞(1)
4𝜋𝜀0 𝑟𝑛 𝑚
Radius of the nth orbit (rn )
The angular momentum of an electron in nth orbit is,
𝐿 = 𝑚𝑣𝑛 𝑟𝑛 − − − 𝑒𝑞(2)
By Bohr’s first postulate, the angular momentum of the electron
L = nh/2π -----eq(2)
where n is an integer and is called as the principal quantum number.
From equations. (2) and (2),
𝑛ℎ
𝑚𝑣𝑛 𝑟𝑛 = − − − −𝑒𝑞(3)
2𝜋
Substituting value of velocity from eq(1)

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1 𝑍𝑒 2 𝑛ℎ
𝑚√ 𝑟𝑛 =
4𝜋𝜀0 𝑟𝑛 𝑚 2𝜋
Squaring on both sides
2
1 𝑍𝑒 2 2 𝑛2 ℎ2
𝑚 𝑟 =
4𝜋𝜀0 𝑟𝑛 𝑚 𝑛 4𝜋 2

𝑛2 ℎ2 𝜀0
𝑟𝑛 = − − − 𝑒𝑞(4)
𝜋𝑚𝑍𝑒 2

From equation (4), it is seen that the radius of the nth orbit is proportional to the square
of the principal quantum number.
Therefore, the radii of the orbits are in the ratio 1 : 4 : 9....
For hydrogen atom, Z = 1 and n = 1 we get r1 = 0.53Å

Energy of an electron in the nth orbit (En)

The total energy of the electron is the sum of its potential energy and kinetic energy in its
orbit. The potential energy of the electron in the nth orbit is given by,
1 −𝑍𝑒 2
𝐸𝑝 =
4𝜋𝜀0 𝑟𝑛
th
The kinetic energy of the electron in the n orbit is,
1
𝐸𝑘 = 𝑚𝑣𝑛2
2
Substituting value of velocity from equation (1)

1 1 (𝑍𝑒)(𝑒)
𝐸𝑘 = 𝑚
2 4𝜋𝜀0 𝑟𝑛 𝑚

1 𝑍𝑒 2
𝐸𝑘 =
8𝜋𝜀0 𝑟𝑛
Total energy = EP + EK
1 −𝑍𝑒 2 1 𝑍𝑒 2
𝐸= +
4𝜋𝜀0 𝑟𝑛 8𝜋𝜀0 𝑟𝑛

−1 𝑍𝑒 2
𝐸=
8𝜋𝜀0 𝑟𝑛
Substituting value of rn from equation(4)
−𝑍 2 𝑚𝑒 4
𝐸= − − − −𝑒𝑞(5)
8𝜀0 𝑛2 ℎ2
From equation (5), it is seen that the radius of the nth orbit is inversely proportional to the
square of the principal quantum number
5

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For hydrogen atom, Z = 1, and substituting other values in equation (5) we get
−13.6
𝐸𝑛 = 𝑒𝑉 − − − −𝑒𝑞(6)
𝑛2
As there is a negative sign in equation (6), it is seen that the energy of the electron in its
orbit increases as n increases.

Frequency of spectral line

According to Bohr’s second postulate, when an electron jumps from an outer orbit of
quantum number n to an inner orbit of quantum number m, the frequency of the photon
emitted is given by,
𝐸𝑚 − 𝐸𝑛
𝜈=
ℎ
Using equation for energy, equation(6)
𝑍 2 𝑚𝑒 4 1 1
𝜈= ( − ) − − − −𝑒𝑞(7)
8𝜀02 ℎ3 𝑛2 𝑚2
The wave number 𝜈̅ of a radiation is defined as number of waves per unit length. It is
equal to reciprocal of the wavelength
1 𝜈
𝜈̅ = = [∵ 𝑐 = 𝜈𝜆]
𝜆 𝑐
From equation(7)
𝑍 2 𝑚𝑒 4 1 1
𝜈̅ = 2 3 ( 2 − 2 ) − − − −𝑒𝑞(8)
8𝜀0 𝑐ℎ 𝑛 𝑚
For Hydrogen Z = 1
𝑚𝑒 4 1 1
𝜈̅ = 2 3 ( 2 − 2 )
8𝜀0 𝑐ℎ 𝑛 𝑚

1 1
𝜈̅ = 𝑅 ( − )
𝑛2 𝑚2

where R is a constant called Rydberg’s constant

Substituting the known values, we get R = 1.094 × 107m-1

Spectral series of hydrogen atom

Whenever an electron in a hydrogen atom jumps from higher energy level to the lower
energy level, the difference in energies of the two levels is emitted as a radiation of
particular wavelength.
It is called a spectral line. As the wavelength of the spectral line depends upon the two
orbits (energy levels) between which the transition of electron takes place, various
spectral lines are obtained.
The different wavelengths constitute spectral series which are the characteristic of
the atoms emitting them. The following are the spectral series of hydrogen atom.
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(i) Lyman series
When the electron jumps from any of the outer orbits to the first orbit, the spectral lines
emitted are in the ultraviolet region of the spectrum and they are said to form a series
called Lyman series
1 1
𝜈̅ = 𝑅 ( 2 − 2 )
𝑛 𝑚
Here n = 1 and m = 2, 3, 4, ….
1
𝜈̅ = 𝑅 (1 − 2 )
𝑚
(ii) Balmer series
When the electron jumps from any of the outer orbits to the second orbit, we get a
spectral series called the Balmer series. All the lines of this series in hydrogen have their
wavelength in the visible region. Here n=2, m = 3,4,5 … The wave number of the Balmer
series is,
1 1
𝜈̅ = 𝑅 ( 2 − 2 )
2 𝑚

The first line in this series (m = 3), is called the Hα-line, the second (m=4), the Hβ-line and
so on.

(iii) Paschen series

This series consists of all wavelengths which are emitted when the electron jumps from
outer most orbits to the third orbit. Here m = 4,5,6 … and n = 3. This series is in the
infrared region with the wave number given by
1 1
𝜈̅ = 𝑅 ( 2 − 2 )
3 𝑚

(iv) Brackett series

The series obtained by the transition of the electron from m = 5, 6...and n = 4 is called
Brackett series. The wavelengths of these lines are in the infrared region. The wave
number is
1 1
𝜈̅ = 𝑅 ( 2 − 2 )
4 𝑚

(v) Pfund series

The lines of the series are obtained when the electron jumps from
any state m = 6, 7... and n=5. This series also lies in the infrared region.
The wave number is,
1 1
𝜈̅ = 𝑅 ( 2 − 2 )
5 𝑚
7

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Shortcomings of Bohr’s theory

Bohr’s theory was able to explain successfully a number of experimental observations and
has correctly predicted the spectral lines of hydrogen atom. However, the theory fails in
the following aspects.
(i) The theory could not account for the spectra of atoms more complex than hydrogen.
(ii) The theory does not give any information regarding the distribution and arrangement
of electrons in an atom.
(iii) It does not explain the experimentally observed variations in intensity of the spectral
lines of the element.
(iv) When the spectral line of hydrogen atom is examined by spectrometers having high
resolving power, it is found that a single line is composed of two or more close
components. This is known as the fine structure of spectral lines. Bohr’s theory could not
account for the fine structure of spectral lines.
(v) It is found that when electric or magnetic field is applied to the atom, each of the
spectral line split into several lines. The former effect is called as Stark effect, while the
latter is known as Zeeman effect.

Excitation and Ionization Potential

Suppose electron revolving in a stationary orbit of an atom absorbs specific energy, and
jumps to an orbit of higher energy. This process is called excitation and the atom is said to
be in the excited state. The energy absorbed to move electron from one orbit to the other
is called excitation potential,
If n = 1 is called ground state, n = 2 is called first excited state, n =3 is called second excited
state
If the energy supplied is large enough to remove an electron from the atom, then the
atom is said to be ionized. The minimum energy needed to ionize an atom is called
ionization energy. Note that energy for n = ∞ is taken as zero.
The minimum amount of energy to release an electron from ground state is called the first
or principal ionization energy. The ionization of electrons from higher energy state is
termed depending on the their quantum number . For n = 2, second ionization energy, for
n = 3, third ionization energy etc.

De Broglie’s explanation of Bohr’s second postulate of quantization

Since the electron do not radiate energy in stationary orbits, the De broglie wave
associated with it must be stationary wave. The electron-wave selects only those orbits
for which the circumference of the orbit is equal to an integral number (n) of the
associated de Broglie wavelength. If it is not then, each wave travel around the orbit will
not be in phase and would interfere in such a way that their average intensity would be
zero. In this case, an electron cannot be found in such an orbit.

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Thus, necessary condition for permitted orbits is
2πr = nλ
Where n = number of waves ( integer) and r = radius of orbit
And λ = wavelength of de Broglie wave = h/mv
𝑛ℎ
∴ 2𝜋𝑟 =
𝑚𝑣
Now angular momentum
𝑛ℎ
𝑙 = 𝑚𝑣𝑟 =
2𝜋

Solved Numerical
Q) The wavelength of the Kα line emitted by a hydrogen atom like element is 0.32Å.
Determine the wavelength of Kβ line emitted by the same element

Solution
From formula for hydrogen like element
1 1 1
𝜈̅ = = 𝑅 ( 2 − 2 )
𝜆 𝑛 𝑚
For Kα n = 1 and m = 2
1 1
= 𝑅 (1 − )
0.32 × 10−10 22
1 3
−10
= 𝑅 ( ) − − − 𝑒𝑞(1)
0.32 × 10 4
For Kβ n = 1 and m = 3

1 1
= 𝑅 (1 − 2 )
𝜆 3
1 8
= 𝑅 ( ) − − − 𝑒𝑞(2)
𝜆 9
Taking ratio of equation (1) and (2) we get
3 9
𝜆 = 0.32 × 10−10 ( ) ( ) = 0.27 × 10−10
4 8
λ = 0.27 Å

Q) Find the relation between three wavelengths λ1, λ2, λ3 from the energy level diagram
shown in figure

Solution
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From figure E3 = E1 + E2 thus
ℎ𝑐 ℎ𝑐 ℎ𝑐
= +
λ3 𝜆1 𝜆2
1 1 1
= +
λ3 𝜆1 𝜆2

𝜆1 𝜆2
λ3 =
𝜆1 +𝜆2
Q) The wavelength of first line of Lyman series of hydrogen is identical to that of the
second line of Balmer series for some hydrogen like ion X. Calculate energies of the first
four levels of X. Also find its ionization potential (Given: Ground state binding energy of
hydrogen atom 13.6 eV)
Solution:
From the formula
1 1 1
= 𝑍2𝑅 ( 2 − 2)
𝜆 𝑛 𝑚
For first line of Lyman series of hydrogen Z = 1, n = 1 and m = 2
1 1 3
= 𝑅 (1 − 2 ) = 𝑅 ( ) − − − 𝑒𝑞(1)
𝜆 2 4
For second line of Balmer series of X, n = 2 and m = 4

1 1 1
= 𝑍2𝑅 ( 2 − 2)
𝜆 𝑛 𝑚

1 1 1 3
= 𝑍𝑅 ( 2 − 2 ) = 𝑍 2 𝑅 ( ) − − − −𝑒𝑞(2)
𝜆 2 4 16
From equation (1) and (2)

3 5
𝑅 ( ) = 𝑍2𝑅 ( )
4 16
Z=2

From the formula for energy of electron in nth orbit

−𝑍 2 𝑚𝑒 4
𝐸=
8𝜀0 𝑛2 ℎ2
For ionization potential n = 1
Ionization potential for H ; Z =1
−𝑚𝑒 4
𝐸𝐻 =
8𝜀0 ℎ2
Ionization potential for X ; Z =2
−22 𝑚𝑒 4
𝐸𝑋 = = 4𝐸𝐻
8𝜀0 ℎ2
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𝐸𝑥 = 4 × (−13.6) = 54.4 𝑒𝑉
Ionization potential of x = 54.4 ev
Energy of ground state or first energy level n=1
−54.4
𝐸2 = = −54.4 𝑒𝑉
12

Energy of first excited state or second energy level n = 2

−54.4
𝐸2 = = −13.6 𝑒𝑉
22
Energy of first excited state or third energy level n = 3
−54.4
𝐸3 = = −6.04 𝑒𝑉
32
Energy of first excited state n = 4 or fourth energy level n = 4
−54.4
𝐸3 = = −3.4 𝑒𝑉
42

Q) A body of mass m is attached at one end of spring of force constant K. It is given a

motion on a circular path of radius r. Assuming that there are integer number of waves
representing this particle on the circumference of the circle and using Bohr’s quantum
condition prove that the quantized energy is given by En = nhω/2π
𝑘
given angular frequency 𝜔 = √
𝑚
Solution:
Total energy = Kinetic energy + spring potential energy
1 1
𝐸 = 𝑚𝑣 2 + 𝑘𝑟 2 − − − −𝑒𝑞(1)
2 2
Here k is restoring force constant of spring and k = mω2 and ω=v/r
𝑚𝑣 2
𝑘= 2
𝑟
On substituting value of k in equation (1) we get
1 1
𝐸 = 𝑚𝑣 2 + 𝑚𝑣 2 = 𝑚𝑣 2 − − − −𝑒𝑞(2)
2 2
According to Bohr’s postulate angular momentum
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
𝑛ℎ𝑣
∴ 𝑚𝑣 2 = − − − 𝑒𝑞(3)
2𝜋𝑟
From equation(2) and (3) we get
𝑛ℎ𝑣
𝐸=
2𝜋𝑟
But ω=v/r
𝑛ℎ𝜔
∴𝐸=
2𝜋
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Q) Suppose the potential energy between electron and proton at a distance r is given
by –ke2/3r3. Use Bohr’s theory to obtain energy levels of such a hypothetical atom
Solution:
We know that for conservative force field
F = -dU/dr
𝑑 𝑘𝑒 2 𝑘𝑒 2 (3) 𝑘𝑒 2
∴𝐹 =− ( )= = 4
𝑑𝑟 3𝑟 3 3𝑟 4 𝑟
Now electrostatic force = centripetal force at equilibrium
𝑘𝑒 2 𝑚𝑣 2
=
𝑟4 𝑟
2
2
𝑘𝑒
∴𝑣 = 3
𝑟
Now according to Bohr’s postulate
𝑛ℎ
𝑚𝑣𝑟 =
2𝜋
Squaring on both sides
2 2 2
𝑛2 ℎ2
𝑚 𝑣 𝑟 =
(2𝜋)2
Substituting value of v

𝑘𝑒 2 2 𝑛2 ℎ2
𝑚2 𝑟 =
𝑟3 (2𝜋)2

𝑚2 𝑘𝑒 2 (2𝜋)2
𝑟=
𝑛2 ℎ2
Now we know that total energy of electron = (1/2) potential energy

𝑘𝑒 2
∴ 𝐸=
6𝑟 3
By substituting value of r from above
𝑘𝑒 2 (𝑛 2 ℎ 2 )3
𝐸=
6 (𝑚2 𝑘𝑒 2 (2𝜋)2 )3

(𝑛ℎ)6
∴𝐸=
6(𝑘𝑒 2 )2 𝑚3 (2𝜋)6

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Q) The energy of an electron in an excited hydrogen atom is -3.4eV. Determine the angular
momentum using Bohr’s theory. Given: Ground state energy of hydrogen atom = -13.6 eV
Solution:
13.6
−3.4 = − 2
𝑛
n=2
Angular momentum
𝑛ℎ 2 × 6.625 × 10−34
𝐿= = = 2.1 × 10−34 𝐽𝑠
2𝜋 2 × 3.14
Q) At what temperature will the average molecular kinetic energy in gaseous hydrogen be
equal to the binding energy of a hydrogen atom? Boltzmann constant kB = 1.3×10-23 JK-1
Solution
3
Kinetic energy of molecule of gas is given by 𝑘𝐵 𝑇
2

3
∴ 𝑘 𝑇 = 13.6𝑒𝑉
2 𝐵

13.6 × 1.6 × 10−19 × 2

𝑇=
3 × 𝑘𝐵

13.6 × 1.6 × 10−19 × 2

𝑇= −23
= 11.16 × 104
3 × 1.3 × 10

𝑇 = 1.116 × 105 𝐾

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