BIOPHYSICS

(BIOT 209)
Lecture:- 01
Electronic Structure of Atom

July 21, 2020

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Outline

1 Introduction

2 Bohr Atom Model

Spectral series of hydrogen atom
Effect of nuclear motion on atomic spectra

3 Assignment

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Introduction

An atom is the smallest particle of chemical elements possessing the

chemical properties of the elements. The first model of an atom is
given by J. J. Thomson. According to his model, an atom is
considered to be a sphere of size 10−10 m and of positively charged
matter in which electrons were embedded. This model could not
explain all features of optical spectra of hydrogen and other elements.
After performing an experiment, Rutherford suggested that the atom
consists of a central massive nucleus of dimension 10−14 m in which
all positive charges and most of the mass are concentrated. A cloud of
negatively charged electrons surround this nucleus. Since the

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Introduction (contd.)

dimension of atom is 10−10 m most of the space of atom is empty.

The nucleus is respossible in repelling the particle.

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Bohr Atom Model

Bohr assumed Rutherford nuclear model of the atom and tried to

overcome the defect of the model giving following postulates:
1 An electron can not revolve round the nucleus in all possible
orbits as suggested by the classical theory. The electron can
revolve the nucleus only in those allowed or permissible orbits
for which the angular momentum of the electron is an integral
h
multiple of or h̄.
2π
2 An atom radiates energy only when an electron jumps from a
stationary orbit of higher energy to one of lower energy. If the
electron jumps from an initial orbit of energy Ei to final orbit of
Ei − Ef
energy Ef (Ei > Ef ), a photon of frequency ν = .
h
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Bohr Atom Model (contd.)

Based on these postulates, Bohr derived two formula for (i) the radius
of the stationary orbit and (ii) the total energy of the electron on the
orbit.
The electrostatic force experienced by an electron at a distance r from
Ze2
nucleus is − . This force provides centripetal force for the
4πε0 r2
electron to revolve round the nucleus i.e.

mv2 Ze2
=
r 4πε0 r2

Ze2
mv2 = (1)
4πε0 r

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Bohr Atom Model (contd.)

According to the first postulate

nh nh
mvr = =⇒ v = (2)
2π 2πmr

Now the equation (1)

2
nh Ze2 n2 h2 Ze2

m = =⇒ =
2πmr 4πε0 r 4π 2 mr2 4πε0 r

Hence the radius of nth permissible orbit is

ε0 h2
 
=⇒ rn = n2 (3)
πZe2 m

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Bohr Atom Model (contd.)

According to quation (3), rn ∝ n2 i.e. the radius of the orbit is in the

ratio of 1 : 4 : 9 : 16 : . . .. The radius of the 1st orbit of hydrogen atom
is

12 × (6.625 × 10−34 )2 × 8.854 × 10−12

r1 = = 0.053 nm
π(1.6 × 10−19 )2 × 9.1 × 10−31

This is called the Bohr radius and the radius of higher orbits are
r2 = 4r1 , r3 = 9r1 and so on.
The total energy of the electron in any orbit is the sum of its kinetic
and potential energies. The potential energy of the electron is
considered to be zero when it is at infinite distance from the nucleus.
Potential energy of an electron in an orbit is given by the work done in
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Bohr Atom Model (contd.)

bringing the electron from infinity to that orbit. This amount of work
done is obtained by integrating the electrostatic force of attraction
between the nucleus and the electron from the limit ∞ to r i.e.
Zr
Ze2 Ze2
P. E. of electron = dr = −
4πε0 r2 4πε0 r
∞

1 1 Ze2
 
K. E. of electron = mv2 =
2 2 4πε0 r
Total energy of the electron in the nth orbit is

Ze2 Ze2 Ze2 Ze2 πZe2 m

 
En = − + =− =−
4πε0 rn 8πε0 rn 8πε0 rn 8πε0 n2 h2 ε0

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Bohr Atom Model (contd.)

Z 2 e4 m
En = − (4)
8ε02 h2 n2
As the value of n increases, En increases. Hence, the outer orbits have
greater energies than the inner orbits.
If an electron jumps from an outer initial orbits n2 of higher energy to
an inner orbit n1 of lower energy, the frequency of the radiation
emitted is given by

En − En1 Z 2 me4 1 1
 
ν= 2 = 2 3 2
− 2 (5)
h 8ε0 h n1 n2

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Bohr Atom Model (contd.)

The wave number ν̄ of a radiation is defined as the reciprocal of its

wavelength λ in vacuum and gives the number of waves contained in
unit length in vacuum, i.e.

1 Z 2 me4 1 1
 
ν
ν̄ = = = 2 3 2
− 2 (6)
λ c 8ε0 h c n1 n2

me4
Let = R and is known as Rydberg constant. In SI unit
8ε02 h3 c

9.1 × 10−31 × (1.6 × 10−1 )4

R= = 1.091×107 m−1
8 × (8.85 × 10−12 )2 × (6.62 × 10−34 )3 × 3 × 108
Therefore,
1 1
 
2
ν̄ = Z R 2 − 2 (7)
n1 n2
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Bohr Atom Model:- Spectral series of hydrogen atom

For hydrogen atom Z = 1 and hence

1 1
 
ν̄ = R 2 − 2 (8)
n1 n2

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

Figure 1: Spectral series of hydrogen atom

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

Lyman series When an electron jumps from second, third etc., orbits
to the first orbit, we get the Lyman series, which lies in
the ultra violet region. Here, n1 = 1 and n2 = 2, 3, 4, . . .
and

1 1
 
ν̄ = R 2 − 2 , n = 2, 3, 4, 5, ldots
1 n

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

Balmier series When an electron jumps from outer orbits to the

second orbit, n1 = 2 and n2 = 3, 4, 5, ldots then

1 1
 
ν̄ = R 2 − 2 n = 3, 4, 5, . . .
2 n

This series is called Balmier series and lies in the

visible region of the spectrum. The first line in the
series (n = 3) is called Hα line, second (n = 4) the Hβ
line and so on.

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

Paschen series Paschen series in the infrared region are given by

n1 = 3 and n2 = 4, 5, 6, . . .

1 1
 
ν̄ = R 2 − 2 , n = 4, 5, 6, . . .
3 n

Bracket series If n1 = 4, n2 = 5, 6, 7, . . ., we get the Bracket series

1 1
 
ν̄ = R 2 − 2 , n = 5, 6, 7 . . .
4 n

Pfund series If n1 = 5, n2 = 6, 7, 8, . . ., we get the Bracket series

1 1
 
ν̄ = R 2 − 2 , n = 6, 7, 8 . . .
5 n

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

Bracket and Pfund series lie in the vary far infrared region of the
hydrogen spectrum. By putting n = ∞ in each one of the series, we
get the wave number of the series limit, i.e. last line in the series.
We have, for hydrogen atom

me4 13.6
En = − = − 2 eV (9)
8ε02 h2 n2 n

me4 9.1 × 10−31 × (1.6 × 10−19 )4

here = =
8ε02 h2 8(8.85 × 10−12 )2 × (6.62 × 10−34 )2
21.76 × 10−19 J = 13.6 eV.
The lowest energy level E1 is called the normal or ground state of the
atom and the higher energy levels, E2 , E3 , . . . are called the excited

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Bohr Atom Model:- Spectral series of hydrogen atom (contd.)

states. As n increases, En increases. As n increases, the energy levels

crowd and forms a continuum.

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Bohr Atom Model:- Effect of nuclear motion on atomic spectra

M r1 r2 m
b b b

N C e

Figure 2: Center of mass system of nucleus and electron

In Bohr theory, we have assumed the nucleus remains fixed at the

center of the circular orbit while the electron revolve round it. This is
true if the nucleus has infinite mass. If the nucleus has mass , both the
nucleus and electron revolve round a common center of mass with
same angular velocity. We let, m be the mass of the electron and M be
the mass of nucleus. C be the center of mass. The nucleus is moving
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Bohr Atom Model:- Effect of nuclear motion on atomic spectra (contd.)

in a circle of radius r1 and electron in a circle of radius r2 . According

to the center of mass theory

Mr1 = mr2

Let r represents the distance between nucleus and electron then

r = r1 + r2

Therefore,

m m m m m
r1 = r2 = (r − r1 ) =⇒ r1 + r1 = r =⇒ r1 = r
M M M M m+M

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Bohr Atom Model:- Effect of nuclear motion on atomic spectra (contd.)

and
M
r2 = r
m+M
The total angular momentum of the atom about the center of mass

L =Mr12 ω + mr22 ω
2 2
m M
 
=M r ω +m r ω
m+M m+M
Mm 2
= r ω = µr2 ω
m+M
Mm
where µ = is called the reduced mass of the electron.
m+M

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Bohr Atom Model:- Effect of nuclear motion on atomic spectra (contd.)

According to the Bohr first principle

h
 
2
µr ω = n (10)
2π

In the absence of nuclear motion, the corresponding equation was

h
 
2
mr ω = n (11)
2π

Equation (10) is identical to Equation (11), except the electron mass

m has been replaced by µ. Therefore, to take into account the finite
mass of the nucleus, we must replace the mass of the electron (m) in

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Bohr Atom Model:- Effect of nuclear motion on atomic spectra (contd.)

all the Bohr formula by the reduced mass. The energy level of
hydrogen atom becomes

µe4 Z 2
En = − (12)
8ε02 h2

When an electron jumps from the Bohr orbit n1 to the Bohr orbit n2 ,
the frequency of the radiation emitted is

µe4 Z 2 1 1
 
ν= 2 3 − (13)
8ε0 h n21 n22

and the wave number is

µe4 Z 2 1 1
 
ν̄ = 2 3 2
− 2 (14)
8ε0 h c n1 n2
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Bohr Atom Model:- Effect of nuclear motion on atomic spectra (contd.)

The Rydberg constant for any element is given by

!
µe4 me4 Mz 1
 
RZ = 2 3 = 2 3 = R∞ (15)
8ε0 h c 8ε0 h c m + Mz 1 + Mmz

me4
where R∞ = is the value ot Rydberg constant when Mz → ∞
8ε02 h3 c
i.e. when the nucleus is at rest and Mz is the mass of the nucleus of the
element of atomic number Z. Equation (14) can now be written as

1 1
 
2
ν̄ = RZ Z − (16)
n21 n22

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Assignment

1 Calculate the radius and energy of the electron in the nth orbit in
hydrogen from the following data. e = 1.6 × 10−19 C,
m = 9.1 × 10−31 kg, h = 6.62 × 10−34 Js, ε0 = 8.85 × 10−12
Fm−1 , c = 3 × 108 m
2 Calculate
1 the wave number
2 wavelength
3 frequency

of Hα line of hydrogen, assuming that the nucleus has infinite

mass. Find the wavelength of Balmier series.

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Assignment (contd.)

3 Show that the velocity of the electron in the first Bohr orbit is
1
c where c is the velocity of the light.
137
4 Determine the separation of the first line of the Balmier series in
a spectrum of ordinary hydrogen and tritium (mass number 3).
Given that R∞ = 10973740 m−1 and mass of the hydrogen
= 1.67 × 10−27 kg

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