586 Principles of Engineering Physics 1

g. The speed of the electron 107 m/s is almost 30 times less than that of light. Hence, we are
permitted to use the classical form of the de Broglie relation to calculate the wavelength.
Thus,

h 6.626 × 10−34
λ
= = m = 0.73 Å
mv 9.11 × 10−31 × 107
Students may calculate the de Broglie wavelength of the electron in this case by applying
the relativistic formula.

Example 7.10
Calculate the kinetic energy of a proton whose de Broglie wavelength is 1.000 femtometers.
Solution
Taking the relativistic form of the de Broglie relation, we have

( 2m c ) + ( 2hc / λ )
2 2
−2m0 c 2 ± 2

( m c ) + ( hc / λ )
0 2 2
K= −m0 c 2 ±
= 0
2

2
Since kinetic energy cannot be negative from this equation, we have

( m c ) + ( hc / λ )
2 2
−m0 c 2 +
K= 0
2

Putting the values of m0 = 1.67 × 10–27 kg (rest mass of proton) and l = 1.000 fm = 1.000 × 10–15 m
into this equation, we get K = 618 MeV.

7.6 Atom Models

Atom is the smallest unit of matter that has the characteristic properties of a chemical
element. As such, the atom is the basic building block of all matter. Structure of atom
had always been one of main targets of scientific communities. The decoding of atomic
structure and development of quantum physics went on parallely. The failures or limitations
of Thomson model (1904), Rutherford model (1911), and Bohr model (1913) in explaining
the observed atomic phenomena completely, played an important role in the groundwork
of quantum physics. Out of the aforementioned three models, Bohr’s model was best,
because interestingly he had incorporated few quantum mechanical concepts intuitively.
Nowadays, the vividly clear picture of atomic or subatomic phenomena can be obtained
simply by solving a second order differential equation called Schrodinger equation! Thus,
quantum physics provided the best model for microscopic particles including photons.

7.6.1 Rutherford’s atom model

J. J. Thomson’s plum-pudding model in which electrons are immersed in a cloud of positive

charge was rejected on the ground that it predicted a single spectral line for the hydrogen
 Elementary Concepts of Quantum Physics 587

atom in contrary to the experimental observation of a series of spectral lines. Rutherford’s

atom model, proposed in 1911 from his famous a-particles scattering experiment, assumed
that the positive charges were highly concentrated inside a small massive sphere called the
nucleus and the electrons were revolving around the nucleus in circular paths. Rutherford’s
atom model was able to explain a lot of experimental observations.
Objections to Rutherford’s atom model
i. However, revolving electrons according to electromagnetic theory should lose energy
by radiating electromagnetic radiation continuously at the rate

1 e2 2
a
6πε o c 3

[a is the acceleration] and finally should fall into the nucleus making the atoms
collapse. It is contrary to the observed fact that atom is a stable entity.
ii. Again according to Rutherford’s model, an atom should emit continuous radiation of
all frequencies which is against the experimental fact that atoms emit spectral lines of
only definite frequencies.
Therefore, Rutherford’s atom model based on classical physics was not fully satisfactory.

7.6.2 Bohr’s atom model

Following the aforementioned serious objections to Rutherford’s atom model, Bohr

suggested some modifications in his model. The model is based on the following basic
postulates.
i. The central part of the atom called nucleus contains the whole of the positive charges;
almost the whole of the mass of the atom is concentrated in it.
ii. Electrons are capable of revolving around the nucleus in certain fixed orbits called
stationary orbits or privileged orbits. The required centripetal force is provided by
the electrostatic force of attraction between the negatively charged electron and the
positively charged nucleus.
iii. Atoms do not radiate energy as long as the electrons are in these certain fixed stationary
orbits.
iv. Atoms radiate energy in the form of quanta when the electrons make transitions from
one stationary orbit to another. The energy carried by one quantum or photon hn is
equal to the energy difference of the two stationary orbits, i.e., hn = E2 – E1.
  
v. The angular momentum L = r × p possessed by an electron in the stationary orbits is
an integral multiple of

h
=
 = 1.054 × 10−34 Js , i.e.,
2π
588 Principles of Engineering Physics 1

L = n, n = 1, 2, 3, 4, …

Here n is called the principal quantum number.

Bohr’s theory of the hydrogen atom
Hydrogen atom consists of one proton (nucleus) and an electron revolving around the
proton/nucleus in a fixed orbit as shown in the Fig. 7.10.

Figure 7.10 Schematic diagram of a hydrogen atom consisting of one proton and one electron.
In the ground state of the atom, the electron stays in the first orbit n = 1. The atom is
said to be in excited state when the electron, by absorbing energy, jumps to higher
h2
orbits with n > 1. This diagram is in conformity with Eq. (7.55) rn = 2 n2 .
4π mke 2
The variation of atomic radius with principal quantum number is parabolic

If radius of the orbit is r the charge of the proton is +e and that of the electron is –e, the
force of attraction Fe between the nucleus and the electron is given by

e×e e2
=Fe k= 2
k 2 (7.51)
r r

1
where in SI system for free space, k = = 9 × 109 Nm2C −2 = with e0 = permittivity of free
space = 8.85 × 10–12 C2m–2N–1 4πε 0
mv 2
This force of attraction Fe produces a centripetal force , where v is the speed of the
r
electron in the orbit and is called orbital speed. Therefore, we can have

mv 2 e2
=k 2
r r
 Elementary Concepts of Quantum Physics 589

e2
or mv 2 = k (7.52)
r
According to Bohr’s postulates, the angular momentum L = mvr possessed by an electron
h
in the stationary orbits of radius r is an integral multiple of , i.e.,
2π
h
L =n
2π

h
or mvr = n (7.53)
2π

Orbital speed of the electron in the nth orbit

The orbital speed of the electron is obtained by dividing Eq. (7.52) by Eq. (7.53) as

e2
vn = 2π k (7.54)
nh

Radius of the nth orbit

The radius of the nth orbit is obtained from Eq. (7.53) as

nh 1
rn =
2π m v

Using the value of v from Eq. (7.54), we get

h2
rn = n2 (7.55)
4π 2 mke 2

Total energy of electron

The total energy possessed by the electron moving in the nth orbit, En is sum of the kinetic
energy, Ek and potential energy, Ep, i.e., En = Ek + Ep
a. The kinetic energy, Ek of the electron is obtained from Eq. (7.52) as

ke 2
Ek =
2r

b. The potential energy Ep of the hydrogen nucleus (a single proton of charge +e)
and the electron system is given by

(e) × (−e) ke 2
Ep = k = −
r r
590 Principles of Engineering Physics 1

Therefore, the total energy possessed by the electron moving in the nth orbit En will be
obtained as

ke 2
En =
Ek + E p =
−
2r

Using the value of r from Eq. (7.48) into this equation, we obtain

2π 2 mk 2 e 4 13.6eV
En =
− 2 2
=
− (7.56)
hn n2

The total energy possessed by the electron moving in the nth orbit En as calculated using
Eq. (7.56) is found to be negative. For the stability of any dynamical system, the total energy
has to be negative. Therefore, the hydrogen atom is stable. When n → •, according to
Eq. (7.56), En = 0. Therefore, when an electron is very far away from the nucleus, its energy
becomes zero and is free from the nucleus.
When electron is in the first orbit (n = 1), its energy is E1 = –13.6 eV and the atom is said
to be in the ground state. When the atom is in any other orbit, the atom is said to be in an
excited state. The energy of the electron when it is in the second orbit (n = 2) is

13.6eV
E2 =
− =
−3.4eV .
22

Figure 7.11 Energy levels of hydrogen atoms in different excited state. The diagram is drawn in
2π 2mk 2e 4 13.6eV
conformity with Eq. (7.56) En =
− =
− .
h2n2 n2
 Elementary Concepts of Quantum Physics 591

If the electron in the ground state of the hydrogen atom absorbs 13.6 eV energy, its
energy will be –13.6 eV + 13.6 eV = 0 and is just free from the nucleus. If the electron in
the ground state of the hydrogen atom absorbs 10.2 eV energy, its energy will be –13.6
eV + 10.2 eV – 3.4 eV = energy of the second level. Hence, the electron by absorbing
10.2 eV energy, will jump to the second orbit.

Example 7.11
Calculate the energy of the electron in the second orbit.
Solution

13.6 eV 13.6
En =
− 2
=
− eV =
−3.4 eV
n 4

Example 7.12
Calculate the angular momentum of the electron, according to Bohr’s theory, in a hydrogen
atom when its energy is –3.4 eV.
Solution
The total energy of the electron when it is in the nth orbit is

13.6 eV
En = −
n2

13.6 eV
Hence, −3.4eV =
− 2
n

or n=2
According to Bohr’s theory, angular momentum L is an integral multiple of  . Hence, we
have

n 2 × 1.054 × 10−34 =
L == 1.108 × 10−34 Js

Energy change during transition

Due to the negative sign in Eq. (7.56), the energy of an electron moving in a higher orbit
(n is greater) is more than that of an electron at lower orbit (n is smaller). Hence, when
an electron jumps from a higher orbit to a lower orbit, excess energy is radiated out in the
form of photons having energy, hn. When an electron jumps from a lower orbit to a higher
orbit, some energy is to be absorbed by the electron, i.e., an electron jumps from a lower
orbit to a higher orbit by absorbing energy. If n1 is a lower orbit of energy
2π 2 mk 2 e 4
E1 = −
h2n12
592 Principles of Engineering Physics 1

and n2 is a higher orbit of energy

2π 2 mk 2 e 4 ,
E2 = −
h2n22

the amount of energy emitted in the form of photons when an electron jumps from n2 to n1
will be E2 – E1. According to Bohr’s postulates,

2π 2 mk 2 e 4  1 1
hν = E2 − E1 =  2− 2
h2  n1 n2 

The frequency n of the radiation emitted when an electron jumps from a higher energy
level to a lower energy level is obtained from this equation as

2π 2 mk 2 e 4  1 1  (7.57)
ν=  2− 2
h3  n1 n2 

1 2π 2 mk 2 e 4  1 1 
or =  2− 2
λ ch3  n1 n2 

1  1 1
or= RH  2 − 2  (7.58)
λ  n1 n2 

2π 2 mk 2 e 4 me 4
where
= RH = = 1.09737315685 × 107 m −1 is called Rydberg’s constant for
ch3 8ε o2 ch3
1
hydrogen atom. Equation (7.58) gives the expression for wave number .
λ
Example 7.13
How much energy is released when an electron in a hydrogen atom jumps from the third orbit
to the second orbit? What is the wavelength of the radiation emitted?
Solution
The total energy of the electron when it is in the third orbit is

13.6 eV 13.6
E3 =
− 2
=
− eV =
−1.5eV
3 9

The total energy of the electron when it is in the second orbit is

13.6eV 13.6
E2 =
− 2
=
− eV =
−3.4eV
n 4
 Elementary Concepts of Quantum Physics 593

The amount of energy released when an electron in a hydrogen atom jumps from the third
orbit to the second orbit is

E = E3 − E2 = 1.9 eV

If n is the frequency, we have

hc 6.626 × 10−34 × 3 × 108

λ
= = = 6539 Å
E 3.04 × 10−19

Limitations of Bohr’s theory

Bohr’s theory successfully explained a number of experimental observations and has correctly
predicted the spectral lines of hydrogen atom, single ionized helium ion and so on in
terms of only the principal quantum number, n. However, Bohr’s theory has the following
limitations
i. The theory does not give any information regarding the distribution and arrangements
of electrons in the atoms.
ii. Spectra of multi-electron atoms cannot be explained by Bohr’s theory.
iii. Bohr’s theory does not explain the variations of intensity of spectral lines.
iv. The theory cannot be used to calculate the rate of transition of electrons from one
level to another level. It is not applicable to the selection rules that apply to them.
v. The theory fails to explain the fine structure of spectral lines.
vi. The theory is not applicable for the quantitative explanation of chemical bonding.
vii. The Zeeman effect [splitting of spectral lines by magnetic fields] and the Stark effect
[splitting of spectral lines by electric fields] cannot be explained by applying Bohr’s
theory.
In spite of all this limitations, Bohr’s theory of the hydrogen atom is a mile-stone in the
development of quantum physics.
Spectral lines of hydrogen atom
According to Eq. (7.56), the energy of an electron moving in a higher orbit is more than
that of an electron at a lower orbit. By absorbing energy from external sources, the electron
jumps to a higher energy level from a lower energy level and the atom is in excited state.
Within a very short time of less than 10–8 s, the electron jumps back to the original lower
energy level by emitting radiations and the atom returns to the ground state. The radiations
of different wavelengths emitted when atoms return to their ground state from the excited
state produce spectral lines. The spectral lines are the bright lines seen against the dark
background or the dark lines seen against the bright background of the spectrometer. They
are the characteristic of the radiation emitting atoms.
594 Principles of Engineering Physics 1

The wavelengths of different spectral lines are calculated using the relation

1  1 1
= RH  2 − 2  [Eq. (7.58)].
λ  n1 n2 
This relation explains the complete spectrum of hydrogen atoms. The wavelengths of the
radiation depend upon the initial and final energy levels between which transition takes
place. Accordingly, a number of series are emitted. Each series is composed of a number of
lines. Detailed accounts of five important series are given here.
Lyman series (n1 = 1)
The Lyman series is composed of the lines which are emitted when electronic transition
takes place to the energy level with the principal quantum number n1 = 1 from all the other
outer energy levels. In other words, the Lyman series is composed of the lines which are
emitted when an electron jumps from the outer energy levels to the first energy level with
principal quantum number n1 = 1. The wavelength of each line of the Lyman series can be
calculated using the formula

1  1
= RH  1 − 2  with n2 = 2, 3, 4, … (7.59)
λLyman  n2 

The wavelength of the first line (n2 = 2) of the Lyman series is obtained using

1  1 O
= 10973731 × 10−10  1 − 2  (A)−1
λLyman −1  2 

O
or λLyman −1 = 1215 A

The wavelength of the second line (n2 = 3) of the Lyman series is obtained as
lLyman–2 = 1025 Å. Similarly, the wavelengths of other lines can be calculated. The wavelength
of the limiting line (n2 = •) of the Lyman series is obtained as lLyman–• = 911 Å.
The Lyman series lie in ultra-violet region of the spectrum.
Balmer series (n1 = 2)
The Balmer series is composed of the lines that are emitted when electronic transition takes
place to the energy level with the principal quantum number n1 = 2 from all other outer energy
levels. In other words, the Balmer series is composed of the lines which are emitted when an
electron jumps from the outer energy levels to the second energy level with principal quantum
number n1 = 2. The wavelength of each line of the Balmer series can be calculated using the formula

1 1 1 
= RH  − 2  with n2 = 3, 4, 5, … (7.60)
λBalmer  4 n2 
 Elementary Concepts of Quantum Physics 595

The wavelength of the first line (n2 = 3) of the Balmer series is obtained by

1 1 1  −1
= 10973731 × 10−10  − 2  (Å)
λBalmer −1 4 3 

or λBalmer-1 = 6561Å

The wavelength of the second line (n2 = 4) of the Balmer series is obtained as
lBalmer–2 = 4860 Å. Similarly, the wavelengths of other lines can be calculated.The wavelength
of the limiting line (n2 = •) of the Balmer series is obtained as lBalmer–• = 3645 Å. Balmer
series lie in the visible and near ultra-violet region of the spectrum.
Paschen series (n1 = 3)
The Paschen series is composed of the lines that are emitted when electronic transition
takes place to the energy level with principal quantum number n1 = 3 from all other
outer energy levels. In other words, the Paschen series is composed of the lines which are
emitted when the electron jumps from the outer energy levels to the third energy level with
principal quantum number n1 = 3. The wavelength of each line of the Paschen series can be
calculated using the formula

1 1 1 
= RH  − 2  with n2 = 4, 5, 6, 7, … (7.61)
λPaschen  9 n2 

The wavelength of the first line (n2 = 4) of the Paschen series is obtained as
lPaschen–1 = 18746 Å. The wavelength of the second line (n2 = 5) of the Paschen series is
obtained by lPaschen–2 = 12815 Å. Similarly, the wavelengths of other lines can be calculated.
The wavelength of the limiting line (n2 = •) of the Paschen series is obtained as lPaschen–• =
8201 Å.
The Paschen series lie in the infra-red region of the spectrum.
Brackett series (n1 = 4)
The Brackett series is composed of the lines that are emitted when electronic transition
takes place to the energy level with principal quantum number n1 = 4 from all other outer
energy levels. In other words, the Brackett series is composed of the lines which are emitted
when the electron jumps from the outer energy levels to the fourth energy level with
principal quantum number n1 = 4. The wavelength of each line of the Brackett series can be
calculated using the formula

1 1 1
= RH  − 2  with n2 = 5, 6, 7, … (7.62)
λBrackett  16 n2 
The wavelength of the first line (n2 = 5) of the Brackett series is obtained as
lBrackett–1 = 40501 Å. The wavelength of the second line (n2 = 6) of the Brackett series is
596 Principles of Engineering Physics 1

obtained as lBrackett–2 = 26244 Å. Similarly, the wavelengths of other lines can be calculated.
The wavelength of the limiting line (n2 = •) of the Brackett series is obtained as
lBrackett–• = 14580 Å. The Brackett series lie in infra-red region of the spectrum.
Pfund series (n1 = 5)
The Pfund series is composed of the lines that are emitted when electronic transition takes place
to the energy level with principal quantum number n1 = 5 from all other outer energy levels. In
other words, the Brackett series is composed of the lines which are emitted when the electron
jumps from outer energy levels to the fifth energy level with principal quantum number n1 = 5.
The wavelength of each line of the Pfund series can be calculated using the formula

1  1 1
= RH  − 2  with n2 = 6, 7, 8, 9, … (7.63)
λPfund  25 n2 

The wavelength of the first line (n2 = 6) of the Pfund series is obtained as
lPfund–1 = 74558 Å. Similarly, the wavelengths of other lines can be calculated. The wavelength
of the limiting line (n2 = •) of the Pfund series is obtained as lPfund = 22782 Å. The Pfund series
lie in the infra-red region of the spectrum.
The emission of all the five important series discussed here are represented
diagrammatically in Fig. 7.12.

Figure 7.12 Representation of Lyman (n1 = 1), Balmer (n1 = 2), Paschen (n1 = 3), Brackett (n1 = 4) and
Pfund (n1 = 5) series diagrammatically
 Elementary Concepts of Quantum Physics 597

Example 7.14
The first line of the Lyman series has wavelength 1215 Å. Calculate the wavelength of the
second line.
Solution
The wavelengths of the first line (n2 = 2) and the second line (n2 = 3) of the Lyman series are
4 9
given respectively by λ1 = and λ2 =
3RH 8RH

λ2 27
Therefore, =
λ1 32

27 27
or λ2 = × λ1 = × 1215 Å = 1025.2 Å
32 32

Example 7.15
Calculate the maximum and minimum wavelengths of the Pfund series.
Solution
The wavelength of the Pfund series is obtained from

1  1 1
= RH  − 2  with n = 6, 7, 8, 9, …
λPfund  25 n2 

The maximum wavelengths of the Pfund series is obtained by putting n2 = 6. Hence, the
maximum wavelength of the Pfund series is given by

1  1 1
= 10973731 × 10−10  − 2  ( Å )
−1

λPfundMax  25 6 

or λPfundMax = 74558 Å

The minimum wavelength of the Pfund series is obtained by putting n2 = •. Hence, the
minimum wavelength of the Pfund series is given by

1  1 1 25
= RH  − =  × 1010 =
Å 22782 Å
λPfundMin  25 ∞  10973731