Quantization of Energy

Theory of atomic model.

Drawbacks of Rutherford model:

i) Rutherford model could not explain the stability of atoms. According to classical
theory of electromagnetism, the electron orbiting the nucleus of Rutherford atom is
in accelerated state and it should emit radiation. As such, its energy should go on
decreasing, resulting into a gradually decreasing radius of the orbit until the electron
collapses into the nucleus. However no such situation has been observed.
ii) This theory could not also explain the line spectra observed in elements like
hydrogen.
Bohr’s Atomic Model: Neil Bohr, in 1913, added the following postulates to Rutherford
model in order to overcome its drawbacks.
1. An electron is allowed to revolve around the nucleus only in certain permitted orbits, in
which it does not radiate any energy. Such orbits are known as the stationary orbits.
2. The permitted orbits are those in which the angular momentum (L = mvr) of the electron is
an integral multiple of h/2π. That means-
h
mvr = n(2π), where n = 1, 2,3,…….

This is called Bohr’s quantization condition.

3. An electron radiates energy only when it jumps from a higher energy level (Ef) to a lower
energy level (Ei). The difference of energy between two levels is equal to the energy of the
photon emitted: hν = Ef – Ei
This is called Bohr’s frequency condition.
Bohr’s Theory of Hydrogen (H) and Hydrogen like (He +, Li++) atoms. (Imp)

Consider a simple hydrogen like atom of atomic number Z, where the single electron of charge
e is orbiting around the nucleus of charge +Ze in a circular orbit of
radius r. The electrostatic force of attraction of nucleus on the v
(Ze)e Ze2
e
electron is given by: Fe = 4π𝜀 =
o r2 4π𝜀o r2

And, the centripetal force on the electron is- r

mv2 Ze
Fc = r

Where, m is the mass and v is the speed of electron.

For the circular orbit, the centripetal force is provided by the
electrostatic force. So
 Fc = Fe
mv2 Ze2
or =
r 4π𝜀o r2

Ze2
or mv2 = --------------------------(1)
4π𝜀o r

Now,

Radius of Bohr’s orbit:

According to Bohr’s quantization condition,
h
mvr = n(2π)
nh
or v = 2πmr -------------------------- (2)

Substituting this value in equation (1),

nh 2 Ze2
m (2πmr) = 4π𝜀o r
n2 h 2 Ze2
or m 4π2m2 r2 = 4π𝜀o r
𝜀 o n2 h 2
or r= where n = 1, 2, 3,
πZe2 m

Thus for nth Bohr orbit, we write-

𝛆𝐨 𝐧𝟐 𝐡𝟐
rn = -------------------------- (3)
𝛑𝐙𝐞𝟐 𝐦

Calculation of Radii for H-atom

For H atom Z = 1. So,
ε h2
rn = (πeo2 m)n2
2
8.85×10−12 ×(6.62×10−34 )
= ( π (1.6×10−19 )2 ×9.1×10−31 ) n2
= (0.53 × 10−10 ) n2
= 0.53 × n2 Ȧ
Thus, for first orbit, n = 1. So, r1= 0.53 Ȧ
For the second orbit, n = 2. and, r2= 0.53 × 4 Ȧ = 2.12 Ȧ, and so on.

𝜀 o n2 h 2
a) Velocity of Electron: Substituting, r = in equation (2), we obtain-
πZe2 m

nh πZe2 m
v = 2πm×𝜀 2 h2
on

Ze2
or v = 2ε
o nh

b) For hydrogen atom Z = 1. So velocity of electron in nth Bohr orbit is written as-
 𝐞𝟐
vn = 𝟐𝛆
𝐨 𝐧𝐡

(1.6×10−19 )2 1
Calculation of velocity: vn = 2×8.85×10−12 ×6.62×10−34 ×n
1
= 2.19 × 106 × n
c 1
= 3×108
×n
2.19×106

c 1
= (137) n where c is the speed of light in
vacuum.
1
Thus in first orbit of Hydrogen atom, speed of electron is 137 th of the speed of light in
vacuum.
## You may find the frequency of electron in an orbit of hydrogen by using
v
f = 2πr

c) Energy of the electron in nth orbit: The electron moving around the nucleus has both
kinetic and potential energies. So total energy in n th orbit can be written as
En = K. E. + P. E. --------------------- (1)
For the electron in nth orbit of hydrogen atom,
mvn 2 e2
= --------------------- (2)
rn 4π𝜀o rn 2

And from Bohr’s quantization condition:

nh
mvn rn = 2π --------------------- (3)

Dividing equation (2) by (3)

mvn 2 e2 2π
= 2 × nh
rn ×mvn rn 4π𝜀o rn

e2
Or vn = 2𝜀 --------------------- (4)
o nh

Using this value in equation (3)

e2 nh
m 2𝜀 rn = 2π
o nh

𝜀 o n2 h 2
rn = --------------------- (5)
πZe2 m
1
Therefore, its kinetic energy, K. E. = 2 mvn2
2
1 e2
= 2 m (2ε ) (Using eqn. 4)
o nh
 me4
or K. E. = 8𝜀2 n2 h2 --------------------- (6)
𝑜

And, the electrostatic potential energy,

e(−e)
P. E. = 4𝜋ε
o rn

e2 πe2 m
= − 4𝜋ε (ε 2 h2 ) (Using eqn. 5)
o on

me4
or P. E. = − 4𝜀2n2 h2 --------------------- (7)
𝑜

Using equations 4 and 5 in 1, the total energy in the nth orbit of H atom becomes-
me4 me4
En = + (− 4𝜀2 n2 h2 )
8𝜀 2 n2 h2
𝑜 𝑜

𝐦𝐞𝟒
En = − 𝟖𝜺𝟐 𝐧𝟐 𝐡𝟐 --------------------- (8)
𝒐

This gives the energy of the electron in the nth state of Hydrogen atom. The negative sign
means that the electron is bound to the nucleus by an attractive electrostatic field.

Calculation of the energy levels:

The total energy in the nth state can be written as-
me4 1
En = − (8𝜀2 h2 ) n2
𝑜

4
9.1×10−31 ×( 1.6×10−19 ) 1
This gives En = − (8×(8.85×10−12 )2 × (6.62×10−34 )2) n2

1
= −( 21.76 × 10−19 ) n2

21.76×10−19 1
=− eV
1.6×10−19 n2
1
= − 13.6 × n2 eV

Now, For the first orbit, n = 1. So, E1 = -13.6 eV (First energy level)
For the second orbit, n = 2. So, E2 = -13.6/4 eV = -3.4 eV (Second energy level)

For the third orbit, n = 3. So, E3 = -13.6/9 eV = -1.51 eV (Third energy level)
For the fourth orbit, n = 4. So, E4 = -13.6/16 eV = -0.85 eV and so on.
Similarly, for n = ∞, E∞ = -13.6/∞ = 0 eV
The energy levels E1, E2, E3 … are also known as the ground state, first excited state,
second excited state,…. respectively. The energy level E∞ = 0 is known as the Free State,
where the electron no longer remains bound to the nucleus.
d) Excitation Energy and Potentials:
The energy state corresponding to n = 1 is called ground state of the atom, and the
states corresponding to n = 2, 3, 4, …… are known as the excited states. Among the
excited states, n = 2 level is known as the first excited state, n = 3 level is known as the
second excited state, n = 4 is known as the third excited state and so on.
The minimum energy required to excite an electron from the ground state to any
of the excited states is known as the excitation energy. For hydrogen, energy of the
levels corresponding to n = 1, 2, 3, 4, … are E1 = -13.6 eV, E2 = -3.4 eV, E3 = -1.51eV, E4 = -
0.85 eV, … respectively. Therefore, the first excitation energy of hydrogen is equal to E2
– E1 = -3.4 – (-13.6) = 10.2 eV, second excitation energy is equal to E3 – E1 = = -1.51 – (-
13.6) = 12.09 eV. Likewise, third excitation energy is -0.85 – (-13.6) = 12.75 eV and so on.
Now, 1 eV is the energy gained by an electron when it is accelerated through a
potential difference of 1 volt. So the excitation potential of an energy level of an atom is
defined as the electric potential through which an electron has to be accelerated so that
when it collides with the atom, the atom is excited to that energy level. It means that, to
excite a hydrogen atom in ground state to the first excited state, the colliding electron
has to be accelerated under a p. d. of 10.2 volts, so that its energy will be equal to the
first excitation energy, i.e. 10.2 eV. Therefore, the first excitation potential of hydrogen
is 10.2 volts. Similarly, second excitation potential is equal to 12.09 volts, third excitation
potential is 12.75 volts, etc.

e) Ionization energy and Ionization potential. The minimum energy required to ionize an
atom, that is, to excite the atom from ground state (n =1) to the Free State (n =∞) is
known as ionization energy. Again, the ionization potential of an atom is defined as the
potential through which an extra electron is to be accelerated so that when it collides
with the atom, the atom is ionized.
For hydrogen, ground state energy E1 = -13.6 eV, and the Free State energy, E∞ = 0 eV.
Therefore, its ionization energy is equal to E∞ - E1 = 0 – (-13.6) = 13.6 eV. In order to gain
this much energy, an electron needs to be accelerated under a p. d. of 13.6 volts.
Therefore, the ionization potential of hydrogen is 13.6 volts.

f) Energy Level Diagram of Hydrogen: A diagram showing different energy levels of

hydrogen with their relative spacing is called its energy level diagram. The energy of
me4 1 1
different states of hydrogen are given by: En = − (8𝜀2 h2 ) n2 = − 13.6 × n2 eV. This
𝑜
gives: E1 = -13.6 eV, E2 = -3.4 eV, E3 = -1.51 eV, E4 = -0.85 eV, E5 = -0.51
eV,……………..and E∞ = 0 eV. So the energy level diagram of hydrogen will be as shown in
the figure below:
 0 n=∞

-0.39 n =6
-0.54 n =5

-0.85 n =4

-1.51 n =3
Energy (eV)

-3.4 n =2

-13.6 n =1
Ground Level
The diagram shows that at the large values of n, the energy values are so close that they
form an energy continuum. At n =∞, the electron is no longer bound to the nucleus and it
becomes a free electron.

Spectral Series of Hydrogen: When an electron jumps from a higher orbit with n = n2 to a lower
orbit with n = n1, it emits energy in the form of radiation. The energy of radiation emitted is
equal to the difference between the energy of two levels. Thus, radiated energy-
hν = En2 − En1 --------------------- (1)

Where ν is the frequency of radiation emitted.

From Bohr’s theory of hydrogen atom, we have-

me4 1
En1 = − (8𝜀2 h2 ) n2
𝑜 1

me4 1
And, En2 = − (8𝜀2 h2 ) n2
𝑜 2

Therefore, from equation (1)

me4 1 me4 1
hν = − (8𝜀2h2 ) n2 + (8𝜀2h2 ) n2
𝑜 2 𝑜 1

me4 1 1
or hν = 8𝜀2 h2 (n2 − n2 )
𝑜 1 2

Since speed of light, c = λν, where λ is the wavelength of radiation emitted,

c me4 1 1
hν = h 𝜆 = 8𝜀2h2 (n2 − n2 )
𝑜 1 2
 1 me4 1 1
giving- = 8𝜀2 ch3 (n2 − n2 )
λ 𝑜 1 2

1 1 1
or = R y ( n2 − n2 ) --------------------- (2)
λ 1 2

me4
Here, R y = 8𝜀2 ch3 is a constant quantity having value equal to 1.097×107 m-1 and is known
𝑜
as Rydberg’s constant.
With different values of n1 along with n2 , equation (2) gives rise to a series of spectral
lines, known as spectral series of hydrogen. They are:
i) Lyman series: This series corresponds to the transitions of electron from n2 = 2, 3, 4, …..
to n1 = 1. Thus for Lyman series,
1 1 1
= 𝑅𝑦 (12 − 𝑛2 ) with n2 = 2, 3, 4, …..
𝜆 2

The spectral lines in this series lie in the ultra violet (uv) region.
ii) Balmer series: This series corresponds to the transitions of electron from n2 = 3, 4,
5,….. to n1 = 2. Thus for Balmer series,
1 1 1
= 𝑅𝑦 (22 − 𝑛2 ) with n2 = 3, 4, 5,…..
𝜆 2

The spectral lines in this series lie in the visible region.

n=∞
n =6
n =5
Pfund Series
n =4
Brackett Series
n =3
Paschen Series

n =2
Balmer
Series

n =1
Lyman
Series

iii) Paschen series: This series corresponds to the transitions of electron from n2 = 4, 5,
6,….. to n1 = 3. Thus for Paschen series,
 1 1 1
= 𝑅𝑦 (32 − 𝑛2 ) with n2 = 4, 5, 6,…..
𝜆 2

The spectral lines in this series lie in the infrared (IR) region.
iv) Brackett series: This series corresponds to the transitions of electron from n2 = 5, 6,
7,….. to n1 = 4. Thus for Brackett series,
1 1 1
= 𝑅𝑦 (42 − 𝑛2) with n2 = 5, 6, 7,…..
𝜆 2

The spectral lines in this series lie in the infrared (IR) region.
v) Pfund series: This series corresponds to the transitions of electron from n2 = 6, 7,…..
to n1 = 5. Thus for Pfund series,
1 1 1
= 𝑅𝑦 (52 − 𝑛2 ) with n2 = 6, 7,…..
𝜆 2

The spectral lines in this series lie in the far infrared (FIR) region.

Emission spectra and Absorption Spectra

The spectra which is obtained due to the transition of electrons from higher energy states to the
lower energy states is called emission spectra. When an electron jumps down from a higher
hc
energy states to lower energy states, the wavelength of the emitted line is given by: = E n2 −
𝜆
En1 . Such spectra is obtained when electric discharge is passed through a discharge tube
containing the experimental gas at low pressure or when atoms in the material are excited by
heating it to a high temperature. The emission spectra of Hydrogen is as shown in fig. 1 below.

n=∞
n =6
Pfund Series n =5
n =4
Brackett series
n =3
Paschen Series

n =2
Balmer Series

n =1
Lyman Series

Fig. 1: Emission spectra of Hydrogen

The absorption spectra is obtained due to the transition of electrons from lower energy states
to higher energy states when light is allowed to pass through a cold, dilute gas. The gas atoms
absorb the photons of particular wavelengths for their excitation and the spectral lines
corresponding to these wavelengths are found missing from the resulting spectrum. These
absorbed wavelengths appear as dark lines in the spectrum. If an atom is excited from a lower
energy state to a higher energy state, the wavelength of absorbed photon is given by:
hc
= E n2 − E n1
𝜆

n=∞
n =6
n =5
Pfund Series
n =4
Brackett Series

n =3
Paschen Series

n =2
Balmer Series

Lyman Series n =1

Fig. 2: Absorption spectra of Hydrogen

Limitations of Bohr’s theory

1. It does not explain about the observed fine structure in Hydrogen spectrum, where
an apparently single spectral line is actually composed of two or more closely
spaced lines.
2. It fails to explain the spectra of complex atoms containing more than one
electrons.
3. It does not predict about the relative intensities of spectral lines.

To account for these limitations Bohr-Sommerfeld atomic model was introduced, which
uses the concept of elliptical orbits. The circular orbits are only the special case of these
elliptical orbits.

De Broglie Hypothesis: Wave-Particle Duality of Matter

Light (or Radiation) behaves as wave in the phenomenon like Interference, Diffraction,
Polarization etc, and as particle in the phenomenon like Photoelectric Effect, Compton Effect
etc. It means that light behaves both as wave and as particle.

In 1924, de Broglie suggested that not only light, matter should also possess dual nature on the
basis of following facts:
i. Total energy density of universe exists both as radiation and matter. As radiation
has dual nature, matter should as well.
ii. Nature loves symmetry. So just like radiation, matter should also have a dual
nature.
 According to him, a particle having a linear momentum equal to ‘p’ has an associated
wavelength ‘λ’ given by:

h
𝜆=p

Where h is Planck’s constant. The wavelength given by this equation is known as de Broglie
wavelength.

Examples: de Broglie wavelength of electron or proton:

Let, mass of particle = m

Charge of the particle = e

If the particle is accelerated by a p. d. equal to V,

1
Gain in kinetic energy, m𝑣 2 = eV
2

𝟐𝐞𝐕
or, its speed, 𝒗 = √ 𝐦

h h
Now, de Broglie wavelength, 𝜆 = p = m𝑣

h m
or, 𝜆 = m √2eV

h
or, 𝜆=
√2meV

For electron, m = me = 9.1 × 10−31 kg

For proton, m = mp = 1.67 × 10−27 kg
h
So, 𝜆e = for electron. And,
√2me eV
h
𝜆p = for proton.
√2mp eV
Q(1). Calculate de Broglie wavelength for (i) proton and (ii) electron, accelerated through the p.
d. of 1 KV
Q(2). If matter has wave nature, why don’t we observe it when a ball is falling?

Heisenberg’s Uncertainty Principle

In 1927, German Physicist Werner Heisenberg developed a principle which states that- “It is
impossible to determine precisely and simultaneously the values of the canonically conjugate
variables”.
This is known as Heisenberg’s Uncertainty principle. The canonically conjugate variables refers
to the pair of physical quantities which describe the motion of an atomic system. Position (𝑥)
and momentum (p), energy (E) and time (t) etc are examples of such variables.

According to this principle, the position(𝑥) and momentum(P) of a particle can’t be determined
simultaneously with a perfect accuracy. If ∆𝑥 is the uncertainty in position and ∆p is the
uncertainty in momentum then these uncertainties are limited by the relation,
h
∆𝑥 × ∆p ≥ 2𝜋

Likewise for the measurement of energy(E) and time(t), uncertainty principle will be
h
∆E × ∆t ≥ 2𝜋

Applications:

This principle can be used to show how an electron can’t exist inside the nucleus, to estimate
the ground state energy of a system, etc.

Q. By using Heisenberg’s uncertainty principle, show that an electron can’t exist in nucleus.

The size of nucleus is ~10−14 m. If electron exists inside nucleus it can stay anywhere within it.
So, maximum uncertainty of its position in nucleus would be ∆𝑥 = 10−14 m
The size of nucleus is ~10−14 m. If electron exists inside nucleus it can stay anywhere within it.
So, maximum uncertainty of its position in nucleus would be ∆𝑥 = 10−14 m
According to Heisenberg’s uncertainty principle, the uncertainty in momentum of the electron
h
is given by (∆𝑥)(∆p) ≥ 2𝜋
h
or ∆p ≥
2𝜋∆𝑥
6.626×10−34
or ∆p ≥ 2𝜋×10−14 = 1.055 × 10−20 kgm/s
It means, the momentum of electron should at least be equal to 1.055 × 10−20 kg m/s. That is-
p > 1.055 × 10−20 kg m/s, or me v = p >
−20
1.055 × 10
Where me is mass and v is the speed of electron.
1.055×10−20 1.055×10−20
Therefore, speed of electron, v > = = 1.6 × 1010 m/s which is greater
me 9.1×10−31
than the speed of light c, and is impossible.
Thus, it is clear that an electron can never exist inside the nucleus.

List of Formulae
h
1. Bohr’s quantization of angular momentum: L = n 2𝜋 , where n = 1,2,3,….
ε h2 2
2. Radius of Bohr orbits: rn = (πeo2 m)n
𝑒2
3. Speed of electron in nth orbit: v =
n 2𝜀𝑜 𝑛ℎ
 me4
4. Kinetic energy of electron in nth orbit: K. E. = 8𝜀2 n2 h2
𝑜
me4
5. Potential energy of electron in nth orbit: P. E. = − 4𝜀2 n2 h2
𝑜
me4 1
6. Total energy of electron in nth orbit: E = − 8𝜀2 n2 h2 = −( 21.76 × 10−19 ) J
𝑜 n2
− 13.6
= eV
n2
me4 1 1
7. Frequency formula for hydrogen spectra: ν = 8𝜀2 h3 (n2 − n2 )
𝑜 1 2
1 me4 1 1
8. Wavelength formula for H spectra(Wave number): 𝜈̅ = 𝜆 = 8𝜀2 ch3 (n2 − n2 )
𝑜 1 2
1 1 7 -1
= Ry ( − ) where, R y=1.097×10 m
n21 n22
9. Spectral series formula:
a. Lyman Series: n1 = 1, n2 = 2, 3, 4,…………
b. Balmer Series n1 = 2, n2 = 3, 4, 5,…………
h h
10. De Broglie wavelength, 𝜆 = p = mv
h
11. Heisenberg’s Uncertainty: (∆𝑥 )(∆p) = for position and momentum
2𝜋
h
and, (∆E)(∆t) = for energy and time.
2𝜋

Numerical problems
1) An electron of energy 20 eV comes into collision with a hydrogen atom in its ground
state. The atom is excited into a state of higher internal energy and the electron is
scattered with reduced velocity. The atom subsequently returns to its ground state with
emission of a photon of wavelength 1.216 × 10−7 m. Determine the velocity of the
scattered electron. (e = 1.6 × 10−19 C, c = 3 × 108 m/s, h = 6.625 × 10−34 Js, me =
9.1 × 10−31 kg)
(Here, Energy of incident electron = Energy of radiated photon + Energy of the scattered
electron)
2) Use Balmer’s formula to calculate the (a) wavelength (b) frequency and (c) photon
energy for the H𝛾 line
3) Find the angular momentum and orbital period of electron in the state where its energy
is equal to -1.51 eV in H atom.
4) Rydberg’s constant is equal to R y = 1.09678 × 107 per meter. Calculate the wavelength
of first member of Balmer Series.
5) Find the de Broglie wavelength associated with a cricket ball of mass 400 g moving with
a speed of 120 km/hr.
6) The first member of Balmer series of hydrogen atom has a wavelength of 6563 angstrom
units. Calculate the wavelength of second member.
(Ans: 4861.5 au)
7) In the singly ionized helium atom, a single electron orbits the nucleus. What is the radius
of the first Bohr orbit for this ion? (Z=2 for helium)
(Ans:0.265 angstrom units)
Students are advised to practice more numerical problems, MCQs and conceptual questions from the book