Introduction to the Bohr Model

Bohr model of the atom was proposed by Neil Bohr in 1915. It came into existence with the
modification of Rutherford‟s model of an atom. Rutherford‟s model introduced the nuclear
model of an atom, in which he explained that a nucleus (positively charged) is surrounded by
negatively charged electrons.

Bohr modified this atomic structure model by explaining that electrons move in fixed orbital‟s
(shells) and not anywhere in between and he also explained that each orbit (shell) has a fixed
energy level. Rutherford basically explained the nucleus of an atom and Bohr modified that
model into electrons and their energy levels.

Bohr‟s model consists of a small nucleus (positively charged) surrounded by negative electrons
moving around the nucleus in orbits. Bohr found that an electron located away from the nucleus
has more energy, and electrons close to the nucleus have less energy.

Postulates of Bohr’s Model of an Atom

In an atom, electrons (negatively charged) revolve around the positively charged nucleus in a
definite circular path called as orbits or shells.

Each orbit or shell has a fixed energy and these circular orbits are known as orbital shells.

The energy levels are represented by an integer (n=1, 2, 3…) known as the quantum number.
This range of quantum number starts from nucleus side with n=1 having the lowest energy level.
The orbits n=1, 2, 3, 4… are assigned as K, L, M, N…. shells and when an electron attains the
lowest energy level it is said to be in the ground state.

The electrons in an atom move from a lower energy level to a higher energy level by gaining the
required energy and an electron moves from a higher energy level to lower energy level by
losing energy.Bohr‟s Model of an Atom

Limitations of Bohr’s Model of an Atom

Bohr‟s model of an atom failed to explain the Zeeman Effect (effect of magnetic field on the
spectra of atoms).

It also failed to explain the Stark effect (effect of electric field on the spectra of atoms).

It violates the Heisenberg Uncertainty Principle.

It could not explain the spectra obtained from larger atoms.

Atomic spectrum of hydrogen atom: Rydberg Equation

We all know that electrons in an atom or a molecule absorb energy and get excited, they jump
from a lower energy level to a higher energy level and they emit radiation when they come back
to their original states. This phenomenon accounts for the emission spectrum through hydrogen
too, better known as the hydrogen emission spectrum.

In the late 1800s, it was known that when a gas is excited using an electric discharge and the
light emitted is viewed through a diffraction grating; the spectrum observed consists not of a
continuous band of light, but of individual lines with well-defined wavelengths. Experiments
have shown that the wavelengths of the lines were characteristic of the chemical element
emitting the light. They were an atomic fingerprint which resulted from the internal structure of
the atom.

What is Hydrogen spectrum?

The hydrogen spectrum is an important piece of evidence to show the quantized electronic
structure of an atom. The hydrogen atoms of the molecule dissociate as soon as an electric
discharge is passed through a gaseous hydrogen molecule. It results in the emission of
electromagnetic radiation initiated by the energetically excited hydrogen atoms. The hydrogen
emission spectrum comprises radiation of discrete frequencies. These series of radiation are
named after the scientists who discovered them.

Hydrogen spectrum wavelength

When a hydrogen atom absorbs a photon, it causes the electron to experience a transition to a
higher energy level, for example, n = 1, n = 2. When a photon is emitted through a hydrogen
atom, the electron undergoes a transition from a higher energy level to a lower, for example, n =
3, n = 2. During this transition from a higher level to a lower level, there is the transmission of
light occurs. The quantized energy levels of the atoms, cause the spectrum to comprise
wavelengths that reflect the differences in these energy levels. For example, the line at 656 nm
corresponds to the transition n = 3 n = 2.

Hydrogen transitions

Hydrogen emission spectrum:

In the year 1885, on the basis of experimental observations, Balmer proposed the formula for
correlating the wave number of the spectral lines emitted and the energy shells involved. This
formula is given as:
This series of the hydrogen emission spectrum is known as the Balmer series. This is the only
series of lines in the electromagnetic spectrum that lies in the visible region. The value, 109,677
cm-1, is called the Rydberg constant for hydrogen. The Balmer series is basically the part of the
hydrogen emission spectrum responsible for the excitation of an electron from the second shell to
any other shell. Similarly, other transitions also have their own series names. Some of them are
listed below,

 Transition from the first shell to any other shell – Lyman series
 Transition from the second shell to any other shell – Balmer series
 Transition from the third shell to any other shell – Paschen series
 Transition from the fourth shell to any other shell – Bracket series
Transition from the fifth shell to any other shell – Pfund series

Hydrogen spectrum series

Johannes Rydberg, a Swedish spectroscopist, derived a general formula for the calculation of
wave number of hydrogen spectral line emissions due to the transition of an electron from one
orbit to another. The general formula for the hydrogen emission spectrum is given by:

Where,
n1 = 1,2,3,4 …
n2 = n1 +1
ν= wave number of electromagnetic radiation. The value 109,677 cm-1 is known as Rydberg
constant for hydrogen.
Sommerfeld atomic model –

This model explains the fine spectrum of Hydrogen atom.The important postulates of
Sommerfeld atomic model are-

1) The orbits may be both circular or elliptical.

2) When path is elliptical , then there are two axis – major axis & minor axis. When length of
major & minor axis become equal then orbit is circular.

3) The angular momentum of electron moving in an elliptical orbit is kh/ 2π.

k is an integer except zero.

Value of k = 1,2,3,4…..
n/k = length of major axis / length of minor axis

With increase in value of k , ellipticity of the orbit decreases. When n= k,then orbit is circular.

source : nptel

4) Sommerfeld suggested that orbits are made up of sub energy levels . These are s,p,d,f. These
sub shells possess slightly different energies.

Bohr gave a quantum number ‘n’ , which determines the energy of electron.

Sommerfeld introduced a new quantum number called Orbital or Azimuthal Quantum number ( l
) which determines the orbital angular momentum of electron.

Values of l =0 to (n-1)

For, n=1 ; l=0 ; 1s su

n=2 ; l=0,1 ; 2s , 2p sub shell

n=3 ; l=0,1 ,2 ; 3s , 3p , 3d sub shell

n=4 ; l=0, 1, 2 , 3 ; 4s , 4p , 4d , 4f sub shell

source : Readorrefer.in

5) When an electron jumps from one orbit to another orbit, the difference of energy (ΔE )
depends upon sub energy levels.

6) It explains the splitting of individual spectral lines of hydrogen & thus fine spectrum . It could
not predict the exact number of lines which are actually present in the fine spectrum.

Defects of Sommerfeld atomic model-

1) This model does not explain the behavior of system having more than one electron.

2) This model does not explain the Zeeman & Stark effect.

De-Broglie Waves

Classical physics predicts electron should “spiral in” to the nucleus emitting continuous spectrum of radiation
as the atom “collapses”. Classical physics can‟t give us stable atoms.
In 1924, the French physicist Louis de Broglie proposed that moving objects behave like waves; these are
called Matter Waves.
De Broglie waves represent the set of waves which establish or reveal the nature and conduct of some atoms,
molecules or some elementary particles under certain circumstances.
The de Broglie Wavelength is denoted by λ and is written as,

Here the symbols have the following meanings.

„h‟ stands for Planck constant

„m‟ denotes the mass
„v‟ is the velocity of the particle
So, the momentum of „p‟ will be,

Hence, the De Broglie relation shows that the wavelength is proportional to the momentum of the particle.
The frequency of the waves has also been deduced by Broglie and he has proved it to be directly proportional
to the total energy E of the particle(where E is the sum of potential and kinetic energy).
The French Physicist Louis de Broglie, in 1924 suggested that besides the particle properties,
particles may also exhibit wave properties. It took around three years to spot the wave nature of
electrons. These waves are also called as matter waves and they demonstrate the properties of a
material object which tend to change in time or space in accordance with the mathematical
equations which illustrate these waves. De Broglie waves play a vital and commendable role but
only in the case of subatomic particles.
An electron can circle a nucleus only in orbits that contain a whole number of de Broglie
Wavelengths. The quantum number n of an orbit is the number of electron waves that fit into the
orbit.
It is only due to the Broglie waves that subatomic particles can be found in otherwise unexpected
cases. The reason behind this is the ability of these waves to penetrate barriers.
The Broglie waves around a closed loop just like the waves coupled with electrons attached to
the nuclei in atoms can continue to stay provided the waves fit perfectly around the loop, else
they cancel out themselves. It is this necessity that forces the electrons in atoms to opt for some
specific structures or arrangements out of the many which would have been there otherwise.

It was in 1925, even before the discovery of electron diffraction that De Broglie proposed the
concept of wavelength λ of waves associated with particles like electrons and photons. If „p‟ I the
momentum of these particles then it is given by
λ = h/p = h/mv
The wavelength associated with an electron accelerated through a potential difference of V volt
is given by
1/2 mev2 = eV or v = √2eV/me
Problem 1
An electron and a photon have same wavelength. If p is the momentum of electron and E is the
energy of photon. The magnitude of p/E in S.I unit is
(a) 3.0 108 (b) 3.33 10-9
(c) 9.1 10-31 (d) 6.64 10-34
Solution:-
As we know that, for electron, λ = h/p
or, p = h/λ
and for photon E = hc/λ
Thus, p/E = 1/c = 1/(3 108 m/s)
= 3.33 10-9 s/m
Therefore, from the above observation we conclude that, option (b) is correct.

Problem 2:-
A particle of mass m is confined to a narrow tube of length L. Find
(a) The wavelengths of the de-Broglie wave which will resonate in the tube,
(b) The corresponding particle momenta, and
(c) The corresponding energies.
Solution:-

(a) The de Broglie waves will resonate with a node at each end of the tube.
A few of the possible resonance forms are listed below:
λn = 2L / n; = 1, 2, 3, ...
(b) Since de-Broglie wavelengths are
λn = h / pn
∴ pn = h / λn = nh / 2L n = 1, 2, 3, ...
(c) (KE)n = Pn2 / 2m = n2h2/8L2m, n = 1, 2, 3, ...
Problem 3:-
What is the energy and wavelength of a thermal neutron?
Solution:-
By definition, a thermal neutron is a free neutron in a neutron gas at about 20°C (293 K).
KE= 3/2 kT = 3/2 (1.38 × 10–23) (293) = 6.07 × 10–21 J
λ = h/p = h/√2m0 (KE) = 6/63 × 10–34/√2(1.67 × 10–27) (6.07 × 10–21) = 0.147 nm

Heisenberg’s Uncertainty Principle

All moving objects that we see around us e.g., a car, a ball thrown in the air etc., move along
definite paths. Hence their position and velocity can be measured accurately at any instant of
time. Is it possible for subatomic particle also?
As a consequence of dual nature of matter, Heisenberg, in 1927 gave a principle about the
uncertainties in simultaneous measurement of position and momentum (mass x velocity) of small
particles.
This Principle States:
“It is impossible to measure simultaneously the position and momentum of a small microscopic
moving particle with absolute accuracy or certainty” i.e., if an attempt is made to measure any
one of these two quantities with higher accuracy, the other becomes less accurate.
The product of the uncertainty in position ( x) and the uncertainty in the momentum ( p = m.
v where m is the mass of the particle and v is the uncertainty in velocity) is equal to or
greater than h/4π where h is the Planck‟s constant.
Thus, the mathematical expression for the Heisenberg‟s uncertainty principle is simply written as
x. p > h/4π

Explanation of Heisenberg’s uncertainty principle

Suppose we attempt to measure both the position and momentum of an electron, to pinpoint the
position of the electron we have to use light so that the photon of light strikes the electron and
the reflected photon is seen in the microscope. As a result of the hitting, the position as well as
the velocity of the electron is disturbed. The accuracy with which the position of the particle can
be measured depends upon the wavelength of the light used. The uncertainty in position is ±λ.
The shorter the wavelength, the greater is the accuracy. But shorter wavelength means higher
frequency and hence higher energy. This high energy photon on striking the electron changes its
speed as well as direction. But this is not true for macroscopic moving particle. Hence
Heisenberg‟s uncertainty principle is not applicable to macroscopic particles.
What is Schrodinger wave equation?
Schrodinger wave equation describes the wave function or state function, There are two
types of Schrodinger equations, time-dependent Schrodinger wave equation, and time-
independent Schrodinger wave equation. These equations were presented by Ervin
Schrodinger in 1925.

In classical mechanics, the motion of a body is given by Newton’s second law of motion. But
elementary particles like electron, protons, and photons possess wave properties as well,
therefore another equation instead of Newton’s second law equation ( F=ma) is required for
describing their motion.

The new equation must take into account wave properties of particles and it should,
therefore, be similar to the equation describing wave on strings acoustic waves or
electromagnetic waves. This equation was found in 1926 by the Austrian physicist
Schrodinger and is known after his name as Schrodinger wave equation.

Schrodinger wave equation derivation

Consider a particle of mass “m” moving with velocity “v” in space. Suppose a system of
stationary waves is associated with the particles at any point in space in the neighborhood
of particle.

We know that:
This is the Schrodinger time-independent wave equation.
Wave function and its physical significance
WAVE FUNCTION

If there is a wave associated with a particle, then there must be a function to represent it. This
function is called wave function.

Wave function is defined as that quantity whose variations make up matter waves. It is
represented by Greek symbol ψ(psi), ψ consists of real and imaginary parts.

Ψ=A+iB

PHYSICAL SIGNIFICANCE OF WAVE FUNCTIONS (BORN‟S INTERPRETATION):

Born‟s interpretation

The wave function ψ itself has no physical significance but the square of its absolute magnitude
|ψ2| has significance when evaluated at a particular point and at a particular time |ψ 2| gives the
probability of finding the particle there at that time.

The wave function ψ(x,t) is a quantity such that the product

P(x,t)=ψ*(x,t)ψ(x,t)

Is the probability per unit length of finding the particle at the position x at time t.

P(x,t) is the probability density and ψ*(x,t) is complex conjugate of ψ(x,t)

Hence the probability of finding the particle is large wherever ψ is large and vice-versa.

NORMALIZATION CONDITION

The probability per unit length of finding the particle at position x at time t is

P=ψ*(x,t)ψ(x,t)

So, probability of finding the particle in the length dx is

Pdx=ψ*(x,t)ψ(x,t)dx

Total probability of finding the particle somewhere along x-axis is

∫pdx =∫ ψ*(x,t)ψ(x,t)dx

If the particle exists , it must be somewhere on the x-axis . so the total probability of finding the
particle must be unity i.e.

∫ψ*(x,t)ψ(x,t)dx=1 (1)

This is called the normalization condition . So a wave function ψ(x,t) is said to be normalized if
it satisfies the condition(1)