Atomic Structure

Thomson’s Atomic Model:

J.J. Thomson, discovered negatively charged particles which were later named electrons. He
proposed the famous Thomson atomic model in the year 1898 just after the discovery of
electrons. The positively charged particles are uniformly distributed with electrons arranged in
such a manner that the atom is electrostatically stable. Thomson’s atomic model was also called
as the plum pudding model or the watermelon model. The embedded electrons resembled the
seed of watermelon while the watermelon’s red mass represented the positive charge
distribution.

An important feature of this model is that the mass of the atom is assumed to be uniformly
distributed over the atom. Although this model was able to explain the overall neutrality of the
atom, but was not consistent with the results of later experiments.

Rutherford’s Model of Atoms and Its Limitations

A British Physicist “Ernest Rutherford” proposed a model of the atomic structure known as
Rutherford’s Model of Atoms in 1911. He conducted an experiment where he bombarded α-
particles in a thin sheet of gold. In this experiment, he studied the trajectory of the α-particles
after interaction with the thin sheet of gold. To study the deflection, he placed a screen made up
of zinc sulfide around the gold foil. The observations made by Rutherford contradicted the plum
pudding model given by J.J. Thomson.
It was observed that:
(i) most of the ∝ particles passed through the gold foil undeflected.
(ii) a small fraction of the ∝ particles was deflected by small angles.
(iii) a very few ∝ particles (~1 in 20,000) bounced back, that is, were deflected by nearly 180°.

On the basis of the observations, Rutherford drew the following conclusions regarding the
structure of atom:
(i) Most of the space in the atom is empty as most of the a–particles passed
through the foil undeflected.
(ii) A few positively charged a– particles were deflected. The deflection must be due to
enormous repulsive force showing that the positive charge of the atom is not spread throughout
the atom as Thomson had presumed. The positive charge has to be concentrated in a very small
volume that repelled and deflected the positively charged a– particles.
(iii) Calculations by Rutherford showed that the volume occupied by the nucleus is negligibly
small as compared to the total volume of the atom. The radius of the atom is about 10–10 m,
while that of nucleus is 10–15 m. One can appreciate this difference in size by realising that if
a cricket ball represents a nucleus, then the radius of atom would be about 5 km.

On the basis of above observations and conclusions, Rutherfor d proposed the nuclear
model of atom (after the discovery of protons). According to this model:
(i) The positive charge and most of the mass of the atom was densely concentrated in extremely
small region. This very small portion of the atom was called nucleus by Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a very high speed
in circular paths called orbits. Thus, Rutherford’s model of atom resembles the solar system in
which the nucleus plays the role of sun and the electrons that of revolving planets.
(iii) Electrons and the nucleus are held together by electrostatic forces of attraction.

Limitations of Rutherford Atomic Model:

1) Rutherford proposed that the electrons revolve around the nucleus in fixed paths called
orbits. According to Maxwell, accelerated charged particles emit electromagnetic
radiations and hence an electron revolving around the nucleus should emit
electromagnetic radiation. This radiation would carry energy from the motion of the
electron which would come at the cost of shrinking of orbits. Ultimately the electrons
would collapse in the nucleus. Calculations have shown that as per Rutherford’s model an
electron would collapse in the nucleus in less than 10-8 seconds. So Rutherford’s model
was not in accordance with Maxwell’s theory and could not explain the stability of an
atom.
 2) His model did not say anything about the arrangement of electrons in an atom i.e., how
the electrons are distributed around the nucleus and what are the energies of these
electrons.

Bohr's Atomic Model

Historically, results observed from the studies of interactions of radiations with matter have
provided immense information regarding the structure of atoms and molecules. Neils Bohr
utilised these results to improve upon the model proposed by Rutherford. Two developments
played a major role in the formulation of Bohr’s model of atom.
These were:
(i) Dual character of the electromagnetic radiation which means that radiations possess both
wave like and particle like properties.
(ii) Experimental results regarding atomic spectra which can be explained only by assuming
quantized electronic energy levels in atoms.

Bohr’s atomic model is built upon a set of postulates, which are as follows:
(i) The electrons move in a definite circular paths around the nucleus ( Fig 3.10). He called these
circular paths as orbits and postulated that as long as the electron is in a given orbit its energy
does not change (or energy remains fixed). These orbits were therefore referred to as stationary
orbits or stationary states or non radiating orbits.

(ii) The electron can change its orbit by absorbing or releasing energy. An electron at a lower
(initial) state of energy, Ei can go to a (final) higher state of energy, Ef by absorbing (Fig 3.11) a
single photon of energy given by

E = hv = Ef – Ei
Similarly, when electron changes its orbit from a higher initial state of energy Ei to a
lower final state of energy Ef , a single photon of energy hν is released.

(iii) The angular momentum of an electron of mass me moving in a circular orbit of

radius r and velocity v is an integral multiple of h/2.

mvr = nh
2π
Where n is a positive integer, known as the principal quantum number. It would also imply
that electrons orbited at fixed radii.
By the middle of the 19th century it was well known by chemists that excited hydrogen gas
emitted a distinct emission spectrum. It was noted that the same lines were always present
and that the spacing between these lines became smaller and smaller.

In 1885, the first person to propose a mathematical relationship for these lines was a Swiss
high school physics teacher, J. J. Balmer. We now call hydrogen's visible spectrum the
Balmer series. Balmer's empirical formula exactly matched the experimentalists' observed
wavelengths. In 1888 the physicist Johannes Rydberg generalized the Balmer equation for all
transitions of hydrogen.

1  1 1 
= R 2 − 2 
λ m n 

Derivation of Rydberg's formula using Bohr's model:

In an hydrogen atom, the centripetal force is being supplied by the coulomb force between it
and the proton in the hydrogen nucleus.

mvn2 Ze 2 Ze 2
=k 2 mvn2 = k ...................................... (1)
rn rn rn

From Bohr's postulate, the electron's angular momentum was quantized:

 h 
mvn rn = n  ............................................ (2)
 2π 

Now using equation 1 and 2, one can get :

 h2 
2
rn = n  2  ........................................ (3)
2 
 4π kmZe 

Kinetic energy of the electron in hydrogen atom is (using eq. 1)

1 2 1 ze 2
K .E . = mvn = k .................................... (4)
2 2 rn

Potential energy of the electron in hydrogen atom is

ze 2
P.E. = − k ................................ (5)
rn

Total energy of an electron (K.E. + P.E.)

 1 ze 2 Ze 2 1 Ze 2
En = k −k =− k
2 rn rn 2 rn

Substituting in the value for rn (eq. 3) into this total energy expression yields

 2π 2 k 2 mZ 2 e 4   1  1
En = − 2
  2  = −Κ  2 
 h  n  n 

Now if an electron is falling from Ej, a high energy state, to Ei, a lower energy state

 1 1
∆E j→i = − K  2 − 2 
j i 

The energy released by the electron during de-excitation equals the energy of the emitted
photon

c  1 1  2π 2 k 2 mZ 2 e 4   1 1 
∆E j →i = E photon = hυ = h = − K  2 − 2  = −   2 − 2 
λ j i   h2  j i 

Reaching to Rydberg's formula:

1  1 1  2π 2 k 2 mZ 2 e 4 
= − R  2 − 2 ; R =  
λ j i   ch 3 

limitations of Bohr's Model :

It fails to explain Zeeman effect and stark effect.

It violates the Heisenberg Uncertainty Principle.
It mixes classical and quantum ideas together.

Problems :

Question 1: Calculate the wavelength of emitted light for the transition of energy level n = 4
to energy level n = 1 for the hydrogen transition. In which region of electromagnetic
spectrum does this radiation fall?

Question 2: Calculate the wavelength of the first line in the Balmer series of hydrogen
spectrum.
 Wave Nature of Particle - the de Broglie Hypothesis

In experiments like photoelectric effect and Compton effect, radiation behaves like particles. de
Broglie, a French physicist asked whether in some situations, the reverse could be true, i.e.,
would objects which are generally regarded as particles (e.g. electrons) behave like waves ? In
1924 de Broglie postulated that we can associate a wave with every material object. In analogy
with photons, he proposed that the wavelength associated with such a matter wave is related to
the particle momentum through the relationship

λ= hp

Here h is the Planck's constant.

Experimental confirmation of de Broglie hypothesis was provided in 1926 by Davisson and

Germer, who studied diffraction of a beam of electrons from the surface of a nickel crystal.
Electrons, scattered by the surface of a crystal of nickel metal, displayed a diffraction pattern.
This confirmed the hypothesis of de Broglie.

Problem 1 : Calculate de Broglie wavelength of a proton moving with a velocity of 104m/s.

Problem 2: Calculate the wavelength associated with a cricket ball of mass 0.2 kg moving
with a speed of 30 m/s.

Problem 3: Consider a beam of electron with a speed 5×106m/s and calculate the de Broglie
wavelength.

The Heisenberg uncertainty Principle

The uncertainty principle says that we cannot measure the position (x) and the momentum (p)
of a particle with absolute precision. The more accurately we know one of these values, the
less accurately we know the other. Multiplying together the errors in the measurements of
these values (the errors are represented by the triangle symbol in front of each property, the
Greek letter "delta") has to give a number greater than or equal to half of a constant called "h-
bar". This is equal to Planck's constant (usually written as h) divided by 4π. Planck's constant
is an important number in quantum theory and it has the value 6.626 x 10-34 joule seconds.

h
∆ x .∆ p ≥
4π
 2 2
∆x = x − x

2 2
∆p = p − p

Reason Behind the uncertainty

It is hard to imagine not being able to know exactly where a particle is at a given moment. It
seems intuitive that if a particle exists in space, then we can point to where it is; however, the
Heisenberg Uncertainty Principle clearly shows otherwise. This is because of the wave-like
nature of a particle. A particle is spread out over space so that there simply is not a precise
location that it occupies, but instead occupies a range of positions. Similarly, the momentum
cannot be precisely known since a particle consists of a packet of waves, each of which have
their own momentum so that at best it can be said that a particle has a range of momentum.

Question 1: The uncertainity in the position and velocity of a particle are 10-2m and 5.27 ×
10-24ms-1 respectively. Calculate mass of the particle.

Schrödinger's equation

At the beginning of the twentieth century, experimental evidence suggested that atomic
particles were also wave-like in nature. For example, electrons were found to give diffraction
patterns when passed through a double slit in a similar way to light waves. Therefore, it was
reasonable to assume that a wave equation could explain the behaviour of atomic particles.
Schrodinger was the first person to write down such a wave equation. The Schrödinger
equation is the fundamental equation of physics for describing quantum mechanical behavior.

The time independent Schrodinger equation for one dimension is of the form
− h 2 ∂ 2 Ψ ( x)
+ V ( x)Ψ ( x) = EΨ ( x)
2m ∂x 2
where U(x) is the potential energy and E represents the system energy. The solution to this
equation is the wave function Ψ(x).

The wave function Ѱ(x) has no physical meaning. The Born Interpretation says that the
wavefunction Ψ(x)Ψ*(x)dx will tell us the probability that the particle is located in the region
between x and (x+dx). A region with a large value for Ψ(x)Ψ*(x) will have high probability
for the particle in that region. Thus the probability of finding the particle between two points
a and b is proportional to the integral of the square modulus of the wavefunction, evaluated
between limits of a and b.
To be consistent with the Born interpretation, a wave function has to have certain
characteristics:
Square integrable over all space. (In this way it can be normalized and represent
probability.)
Single-valued (so that the probability at any point is unique).
Continuous at all points in space (if the wave-function is not continuous at some point,
the probability of finding the particle in the interval containing x will not be defined).
First derivative must be continuous at all points where the potential is continuous.

Normalization of the Wavefunction

Suppose a quantum particle is moving only along x-axis. A measurement of the position(x) of
the particle must yield a value between - ∞ and + ∞ , since the particle has to be located
somewhere. The wavefunction is interpreted as follows: Ψ * ( x)Ψ ( x) is the probability density of
a measurement of the particle's displacement yielding the value x. Now, a probability is a real
+∞
number between 0 and 1. The total probability must be 1. ∫ Ψ * ( x ) Ψ ( x ) dx = 1 is generally known
−∞
as the normalization condition for the wavefunction.

Particle in a box (one dimension)

Previously we introduced Schrödinger's equation and the wave function, which contains all the
information there is to know about a quantum system. Now it's time to see the equation in action,
using a very simple physical system as an example.
Suppose you have a particle bouncing back and forth between two walls in a box. Assume that
the particle moves in one dimension only, along the X-axis, between vertical, impenetrable walls
at x=0 and x=L. There are no forces acting on the particle inside the box, so its potential energy
is zero here: V(x,t)=0 for 0<x<L. Infinitely large forces push the particle back when it hits a
wall: the potential energy V(x,t) is infinite for x ≥L and x ≤0.

Now we put the value of potential energy V(x)=0 into the time independent Schrodinger
equation for one dimension form.
− h 2 ∂ 2 Ψ ( x) ∂ 2 Ψ ( x) 8π 2 mEΨ ( x)
= EΨ ( x) + =0
2m ∂x 2 ∂x 2 h2
Any solution to this equation will take the form

 8π 2 mE   8π 2 mE 
Ψ ( x ) = A cos  x + B sin 
 x
 h 2   h 2 
   
Here A and B are constants.
We know that the particle can never be outside the box because it would need an infinite amount
of energy to get there. As Ψ2(x) is the probability of finding the particle at position x and it will
be always zero for x ≥L and x ≤0.
Hence Ψ(x) is zero at x=0 and at x=L.
Now applying x=0 and Ψ(0)=0 in the about equation of Ψ(x).
0 = A cos 0 + B sin 0 A=0

Now Ψ(x) will be following as A=0 :

 8π 2 mE 
Ψ ( x ) = B sin  x
 h 2 
 
Now applying x=L and Ψ(L)=0 in the about equation of Ψ(x).

 8π 2 mE 
0 = B sin  L
 h 2 
 
So either B=0 or sine term is zero. The former is not possible then Ψ(x)=0 everywhere.
 8π 2 mE 
sin  L = 0
 h 2 
 

8π 2 mE
L = 0, π ,2π ,3π ,.....
h2

In other words
8π 2 mE
L = nπ
h2
for n a positive integer. (n=0,1,2,3.....)
This tells us that the energy of the particle can only have discrete values
n2h2
En =
8mL2
The quantum number n=0 corresponds to zero energy - but it also gives a wave function Ψ0(x)
which is zero everywhere in the box, which would mean the particle cannot be anywhere in the
box. Thus, the quantum number n=0 is also ruled out, so the permissible energy levels are for
n=1,2,3,4..........

The wavefunction for a particle in a 1-D The probability distribution for a particle
box at the n=1 and n=2 energy levels. in a 1-D box at the n=1 and n=2 energy