PHY-1203

(Physics-II)

1st Chapter: Atomic Physics

 Models of the Atom
Historical perspective
 400 B.C ─> Democritus thought matter could not be divided
indefinitely. This led to the idea of atoms in a void.

 350 B.C ─> Aristotle modified an earlier theory that matter was made of
four “elements”: earth, fire, water, air. Aristotle was wrong. However, his
theory persisted for 2000 years.
fire
earth air
water
Historical perspective
 1800 ─> Dalton proposed a modern atomic model based on experimentation
not on pure reason.

(i) All matter is made of atoms.

(ii) Atoms of an element are identical.
(iii) Each element has different atoms.
(iv) Atoms of different elements combine in constant ratios to form
compounds.
(v) Atoms are rearranged in reactions.

 His ideas account for the law of conservation of mass (atoms are neither created
nor destroyed) and the law of constant composition (elements combine in fixed
ratios).
 Atomic Model
J. J. Thomson discovered the electron in 1897 by the
measurement of its charge to mass ratio e/m.
 The charge of electron was measured by Millikan in 1906 by his
famous oil-drop experiment.

Various atom models :

1. Thomson’s Plum Pudding model 2. Rutherford’s Nuclear model
3. Bohr’s atom model 4. Sommerfeld’s Relativistic model
5. Vector atom model 6. Wave Mechanical atom model
 Thomson’s Plum Pudding Model
J. J. Thomson’s plum pudding model is the first model of atom.
Thomson in 1904 proposed that the positively charged matter of an atom is
uniformly distributed in a sphere of about 10-10 metre radius in which
negatively charged electrons were uniformly embedded like plums in a
pudding. The electrons were so arranged inside the positive sphere that
their mutual repulsion were exactly balanced by the force of attraction
towards the centre of the sphere.

 Since the electrons are

distributed throughout the
atom like raisins in a plum
pudding, this model is Fig. 1

sometimes known as plum-

pudding model.
 Failure of Thomson’s model
 This model failed to explain all line spectrum of hydrogen and other
elements.
 This model could not explain the scattering of α-particles through thin foils
(experiment of Rutherford ) and hence discarded.

Rutherford’s Experiment on
-particles Scattering
 The experimental arrangement is shown in Fig. 02. High speed -particle are
emitted by some radioactive material like radium or radon or polonium R, kept
inside a thick lead box. D is the lead screen with a small hole in it to select a very
fine beam of -particles. This well collimated beam is then allowed to fall on a
thin gold foil F. While passing through the gold foil, the -particles are scattered
through different angles.
Fig. 02

 A movable zinc sulphide screen was placed on the other side of the gold foil. So
the -particles scattered from the gold foil at angles varying from 0 to 180°. When
an -particle strikes the screen, it produces a flash of light and it is observed by
microscope M. From the experiment, it was found that
1) Most of the -particles passed through the gold foil with small deviation.
2) There were a few particles that were scattered through large angles. Experimental
results showed that one of 8000 particles suffered angles of scattering >90°. A few of
the -particles were even scattered directly in the backward direction (angle of
scattering = 180°). Thomson’s model failed to explain this experimental result.
Therefore, Rutherford pictured an atom model.
 Rutherford’s Nuclear Atom Model

 Rutherford proposed the following model of an atom

1) An atom consists of a small and massive central core in which the entire
positive charge and almost the whole mass of the atom are concentrated. This
core is called the nucleus. Electrons have no place inside the nucleus. The
electrons revolve around this nucleus at some distance away. The dimensions
of the nucleus and of the electrons are negligibly small as compared to the
overall size of the atom, so that most of the volume occupied by an atom is
actually an empty space. Thus the discovery of the nucleus of the atom is due
to Rutherford.
2) Since the electron distribution must give stability to the atom, the electron
could not be stationary. The electrons must be revolving round the nucleus in
closed orbits, so that the centrifuge force due to the rotation of the electrons is
balanced by the force electrostatics attraction between the nucleus and
electrons
 Major Deficiencies of Rutherford’s
Nuclear Atom Model
 It was found later on that Rutherford’s model had two serious drawbacks

1) The stability of the atom as a whole

2) The Rutherford’s model of atom does not say anything about the arrangement of
electrons in an atom.

Rutherford explained that all the positive charge was concentrated at the centre
and the electrons revolved around it. According to Rutherford's theory, electrons
could orbit the nucleus at any distance. When the electrons circle round the
nucleus, they are constantly changing their direction. According to classical
electrodynamics, such electrons which either constantly change their direction or
their velocity or both should continuously emit radiation. While doing so, they
should lose energy. Hence, the electron would fall into the nucleus and the atom
will collapse. This means every atom is unstable, quite contrary to our
observation
 Bohr’s Atom Model
 Bohr’s model retains the two essential features of Rutherford’s planetary model i.e

1) The atom has a massive positively-charged nucleus

2) The negatively charged electrons revolve round their nucleus in circular orbits. The
centrifugal force being balanced by the electrostatic pull between the nucleus and
electrons.

 Neil Bohr extended this model by utilizing Plank's quantum Theory. He made
the following three assumptions:

3) An electron cannot revolve round the nucleus in any arbitrary orbit but in just certain
definite and discrete orbits. Only those orbits are possible (or permitted) for which the
orbital angular momentum of the electron is equal to an integral multiple of h/2 i.e.
angular momentum = nh/2, where n is an integer and h is Plank's constant. Such
orbits are also known as stationary orbits.
4) While revolving in these permitted stationary (or stable) orbits, the electron does not
radiate out any electromagnetic energy. In other words, the permissible orbits are
non-radiating paths of the electrons.
 5) The atom radiates out energy of a particular frequency in whole quanta of amount h.
This can only occur when an electron jumps from one allowed orbit to another. If E1
and E2 are the energies corresponding to two orbits before and after the jump, the
frequency of the emitted photon is given by the relation .

E2  E1  h where,  is the frequency of the emitted radiation.

Fig. 3 (a) Permitted orbits (a) Electron’s jump

 Bohr’s Formulae
 Based on these postulates, Bohr derived the formulae for (i) the radii of the
stationary orbits (ii) the total (orbital) energy of the electron in the orbit.

 Consider an atom whose nucleus has a positive charge Ze and mass M (as in
Fig.4. For hydrogen, Z=1. Let an electron of charge (-e) and mass m move
round the nucleus in an orbit of radius r. Since M»m, the nucleus is stationary.
Hence the mass of the nucleus does not come into the calculation.
The electrostatic force of attraction between the
nucleus and the electron is given by

1 ( Ze)( e)
Fe  ...............(i )
4 0 r 2

The centrifugal force on the electron is given by

mv 2
Fc  ..............(ii )
r
Fig. 04
Since the stable nucleus exists, the system will be stable if Fe = Fc

mv 2 1 Ze2
 .............(iii )
r 4 0 r 2

According to Bohr’s postulate,

nh nh
mvr  Or, v
2 2rm
Substituting the value of v in (iii), we have
2 2 2
m nh 2 2
1 Ze 2
1 nh Ze
( 2 2 2) Or, ( )
r 4 r m 4 0 r 2 r m 0
n h 0 2 2

r  2
Ze  m
Therefore, the radius of the nth permissible orbit for hydrogen is given by

n 2 h 2 0
rn  2 ............(iv )
e m
( since Z = 1 for hydrogen atom)

From equation (iv) we find that rn n2.

The radius of the first orbit for hydrogen atom is

12  (6.625 10 34 ) 2 (8.854 10 12 )

r1  metre  0.053 nm
 (1.6 10 ) (9.11 10 )
19 2 31

This is called the Bohr radius.

The orbital rotational frequency of an electron is
v 1 nh nh
f    2 2
2 r 2r 2rm 4 mr
nh e 4 2 m 2 me4
 2 . 4 4 2  2 3 3 ..............(v)
4 m n h  0 4 0 n h
 Calculation of Total Energy
 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 an
infinite distance from the nucleus. Potential energy of an electron in an orbit is given
by the work done in bringing the electron from infinity to that orbit. This amount of
work is obtained by integrating the electrostatic force of attraction between the
nucleus and the electron from the limits  to r.
Potential energy of the electron is

 Ze2
r
Ze2
P.E .   dr  ................(vi )

4 0 r 2
4 0 r

Kinetic energy of the electron is given by

1 2 Ze2
K .E .  mv  ..............(vii )
2 8 0 r [using equ. (iii) ]
Total energy of the electron in the nth orbit is given by

 Ze Ze 2
 Ze 2 2

En  P.E  K .E   
4 0 r 8 0 r 8 0 r
Substituting the value of r from (iv),

 me4 Z 2  me4
E n  2 2 2  2 2 2 ........(viii ) ( since Z = 1 for hydrogen atom)
8 0 n h 8 0 n h

This expression gives the total energy of an electron when it occupies any one of the
different orbits or shells of the hydrogen atom.
 Electron Energy Levels in Hydrogen Atom
 The orbital energy of an electron revolving in nth orbit is given by
 me4 21.7  10 19 21.7  10 19 1
En  2 2 2   joules  eV
8 0 n h n 2
1.6  10 19
n 2

13.6
 En   2 eV
n
For K-shell, n = 1, then
E1  13.6 eV
For L-shell, n = 2
13.6
E2   2
eV  3.4 eV
2
For M-shell, n = 3
13.6
E3   2 eV  1.51 eV and so on.
3
As the value of n increases, En increases. Hence, the outer orbits have greater energies than
the inner orbits.
 Normal, Excited and Ionized Atom
 Consider the simplest hydrogen atom. When its only electron is in its
innermost orbit (n=1), then the atom is said to be in its normal ( or
unexcited) state.
 When the electron is completely removed from the atom, the atom is said to
be ionized.
 If the electron is forced into an outer or higher n-value orbit, then the atom
is said to be excited (or in an excited state)

 The atom does not remain in the excited state longer than 10-8 second
because the electron under the attractive force of the nucleus jumps to
the lower permitted orbit. In so doing, the electron loses the energy it
had earlier gained during collision.
 Spectral Series of Hydrogen Atom
 When hydrogen atom is excited, it returns to its normal unexcited or ground state
by emitting the energy it had absorbed earlier. This energy is given out by the raised
electron in the form of radiations of different wavelengths as it jumps down from a
higher to a lower orbit. These different wavelengths constitute spectral series which
are characteristic of the atom emitting them. When observed through a
spectroscope, these radiations are imaged as sharp and straight vertical lines of a
single colour.

The frequency of the emitted radiations can be found from the following relation

h  E ni  E n f Here, nf represents a higher energy state and ni

represents a lower energy state

 me4 Z 2 me4 1
Now, En f  2 2 2  2 2 2
8 0 h n f 8 0 h n f
 me4 me4 1
and E ni  2 2 2   2 2 2
8 0 h ni 8 0 h ni
Hence, we can write

me4 1 1 me4 1 1
h  E n f  E ni   2 2 ( 2  2 )  2 2 ( 2  2 )
8 0 h n f ni 8 0 h ni n f

Now, c = , where C is the velocity of light. Hence replacing =c/, we get

hc me4 1 1
 2 2( 2  2)
 8 0 h ni n f

me4
1 1 1 1 1
or ,  2 3 ( 2  2 )  R( 2  2 )
 8 0 h c ni n f ni n f

me 4
where, R  2 3  10.97 106 m 1  Rydberg's constant
8 0 h c

1 11
  R( 2  2 )
 ni n f
 This is the general expression for the wave-length of radiation emitted
by an electron as it jumps from higher orbit nf to lower orbit ni. The different
wavelengths which form different spectral series of hydrogen atom can be
found by giving suitable values to ni and nf.

The different series observed in the hydrogen spectrum are as under:

(a) Lyman Series:

It consists of all those wavelengths which are emitted when an electron jumps
from different higher orbit to the first orbit (n = 1). In other words, all those electronic
jumps which end at K-orbit give rise to Lyman series.
Here, ni = 1 and nf = 2 , 3, 4, ……..

The wave-length of the different members of this series is found from the relation:

1 1 1 1
 R( 2  2 )  R(1  2 )
 1 nf nf
The wave-lengths of different members are as under:

(i) First member: nf =2

1 1 3R
 R(1  ) 
 22 4
4 4
   m
3R 3  10.97  10 6

 1216  10 10 m  1216 A

(ii) Second member: nf =3

1 1 8R
 R(1  ) 
 32 9
9 9
   m
8 R 8  10.97  10 6

 1026  10 10 m  1026 A and so on

 (iii) Limiting member: nf =

1 1
 R(1  2 )  R
 

1 1
  m  912  10 10
m  912 A
R 10.97  10 6

This series of wave-lengths lies in the ultraviolet region of the spectrum.

 (b) Balmer Series:
It consists of all those wave-lengths which are emitted when different electrons
jump from outer orbits to the second (n=2).
Here, ni = 2 and nf = 3, 4, 5 ……..

1 1 1
  R( 2  2 )
 2 nf
The wave-lengths of different members are as under:

(i) First member: nf =3

1 1 1 5R
 R( 2  2 ) 
 2 3 36
36 36
   m  6563  10 10
m  6563 
5R 5  10.97  10 6
 (ii) Second member: nf =4

1 1 1 3R
 R( 2  2 ) 
 2 4 16
66 16
   m  4861  10 10
m  4861  and so on.
3R 3  10.97  10 6

(iii) Limiting member: nf =

1 1 1 R
 R( 2  2 ) 
 2  4
4 4
   m  3646  10 10
m  3646 
R 10.97  10 6

This series lies in the visible and near ultraviolet region of solar spectrum.
 (c) Paschen Series:
The different wave-lengths are given by the relation

1 1 1
 R(  ) where nf = 4, 5, 6, ….. 
 32 2
nf

(d) Brackett Series:

1 1 1
 R( 2  2 ) where nf = 5, 6, 7, ….. 
 4 nf

(e) Pfund Series:

1 1 1
 R( 2  2 ) where nf = 6, 7, 8, ….. 
 5 nf

This three series lie in the infrared region of spectrum.

The spectral series is shown in the figure below:
 Problems:
1. At what speed must the electron revolve round the nucleus of a hydrogen atom in
order that it may not be pulled into the nucleus by electrostatic attraction? Also
calculate its orbital energy and frequency. [2.25×106m/s, 21.710-19 J, 6.71015 Hz]
2. The Rydberg constant for hydrogen is 10.97106 m-1. Calculate the short and long
wave-length limits of Lyman series of hydrogen spectrum. [1216Å, 912 Å]
B
3. Energy in a Bohr orbit is given to be equal to  2 where B = 2.179×10-18 J.
n
Calculate the frequency of radiation when the electron jumps from the third orbit to
the second. [ = 4.6×1016 Hz].
4. Show that the velocity of the electron in first Bohr orbit is (1/137)c, where c is the
velocity of light.
5. Find the wave-length of the photon emitted when the hydrogen atom goes from
n=10 to the ground state. [ 921 Å]
 Deficiencies in Bohr’s Model
 Bohr’s atom model, based on circular electron orbits, was successful in predicting
accurately the positions of the spectral lines of the neutral hydrogen atom and singly-
ionized helium atom in terms of one quantum number called principal quantum
number n. However, it was revealed by refined spectroscopic analysis that the
individual spectral lines were not really single but had a fine structure i.e they
consisted of several very fine lines lying close together. This fine structure of spectral
lines could not be explained on Bohr’s theory. The existence of fine structure suggests
that for a given principal quantum number n, there are several orbits of slightly
different energies.
In brief, certain obvious deficiencies in Bohr’s model is summarized as under:

 The planetary model introduces only one quantum number n whereas experimental
evidence concerning fine structure of spectral lines suggests additional quantum
numbers.
 It applies to one-electron atoms and is not easily extended to describe more
complicated or many-electron atoms.
 It cannot be used for quantitative explanation of chemical bonding.
 Sommerfeld’s Relativistic Model
Sommerfeld succeeded partially in explaining fine structure by extending Bohr’s theory
in two ways:
(i) he allowed the possibility of elliptical orbits for the electrons in addition to
Bohr’s circular orbits.

(ii) he took note of the relativistic variation of electron mass with velocity which
was different at different parts of the elliptical orbits.

Now, when elliptical orbits are permitted, one has to deal with two variables quantities.
In polar coordinates, these are

(a) the varying distance of the electron from the nucleus i.e. r and
(b) the varying angular position of the electron with respect to the nucleus
i.e the azimuthal angle .
To deal with these two variables, we need two quantum numbers:

(i) One is the principal quantum number n of Bohr’s theory which has been
retained. It determines the radii of the orbits and energy of the orbital electron.

(ii) The other is a new quantum number called orbital quantum number l which has
been introduced to characterize the angular momentum of an orbit. It determines
the orbital angular momentum of the electron. Its value varies from zero to (n-1)
in steps of unity.

The orbital quantum number is useful in finding the possible elliptical orbits. Possible
ellipses are such that

b l 1

a n
where a and b are semi-major and semi-minor axes respectively of the ellipse.
 According to Sommerfeld’s model, for any principal quantum number n, there are n
possible orbits of varying eccentricities called sub-orbits or sub-shells. These possible
sub-orbits possess slightly different energies because of relativistic variation of the
electron mass.

For example, for n = 1, number of sub-orbits is 1, for n = 2, the number of possible

sub-orbits is 2 and for n= 3, number of possible sub-orbits is 3 and so on. These
additional possible sub-orbits or sub-shells for a given principal quantum number are
allotted different l-values.
For n =1, only one sub-orbit or sub-shell is possible having l = 0. For n =2, two sub-
orbits are possible having l-values of 0 and 1. For n=3, three sub-orbits or sub-shells are
possible with l=0, 1 and 2 respectively (Fig. 7 ) and so on. Obviously, the orbital
quantum number l can have integral values lying between 0 and (n-1).

In other words, 0  l (n-1)

Fig. 7 shows the possible orbits for values of n from 1 to 4. For example, for n = 4, four sub-shells
are possible.
 Number of Electrons in a Shell
 Electrons which have the same principal quantum number n are said to belong
to the same shell. These shell are also designed by letters. For example, n = 1
shell is called K-shell, n=2 shell is called L-shell and n=3 shell is called M-shell
and so on.

 For a given values of n, electrons having the same orbital quantum number l are
said to belong to the same sub-shell. These sub-shells are also denoted by letters
like s, p, d, f etc. The maximum number of electrons in a sub-shell is given by
2(2l+1) because there are (2l+1) values of ml and two values of ms.

Hence, maximum number of electrons in a shell is given by

l  n 1

 2(2l  1)  (2 1)  (2  3)  (2  5)  ....  2[2(n  1)  1]

l 0

 2[1  3  5  ......  {2(n  1)  1}]

Number of Electrons in a Shell
This represents an arithmetical progression with a common difference of 2, initial
term of 1 and the final term {2(n-1)+1}. The sum of such progression is

n 
2 {2  2(n  1)}  2n 2

2 
Hence, maximum number of electrons in a shell is 2n2. When a shell contains
its maximum possible number of electrons, it is said to be filled or closed.
The same terms are applied to sub-shell as well.
 Vector Atom Model
A model of atomic structure in which spin and orbital angular momenta of the electrons
are represented by vectors.

1. Bohr’s theory able to explain only the series spectra of the simplest hydrogen atom.
It could not explain the multiple structure of spectral lines in the simplest hydrogen
atom. Sommerfeld’s theory was able to give an explanation of the fine structure of
the spectral lines of hydrogen. However, Sommerfeld’s theory could not predict the
correct number of the fine structure lines. Moreover, it gave no information about
the relative intensities of the lines. Somerfeld’s theory could not explain the complex
spectra of alkali metals like sodium.

2. These older theories were inadequate to explain new discoveries like Zeeman Effect
and Stark Effect in which the spectral lines could be split up under the influence of
magnetic and electric fields.

3. Another drawback of the Bohr model was that it could not explain how the orbital
electrons in an atom were distributed around nucleus.
 Vector Atom Model
Therefore, in order to explain the complex spectra of atoms and their relation
to atomic structure, the vector atom model was introduced. The two distinct
features of the vector atom model are:

1. The conception of spatial quantization, and

2. The spinning electron hypothesis

(1) Spatial quantization: According to Bohr’s theory, the orbits are quantized as
regards their magnitude (i.e. their size and form). But according to quantum theory, the
direction or orientation of the orbits in space also should be quantized. To specify the
orientation of the electron orbit in space. We need a fixed reference axis. This reference
line is chosen as the direction of an external magnetic field that is applied to the atom.
The different permitted orientations of an electron orbit are determined by the fact that
the projection of the quantized orbits on the field direction must themselves be
quantized. The idea of space quantization leads to an explanation of Zeeman effect.
(ii) Spinning Electron : To account for the observed fine structure of spectral
lines and to explain the anomalous Zeeman effect, the concept of spinning electron
was introduced. According to this hypothesis, the electron spins about an axis of its
own, while it also moves round the nucleus of the atom in its orbit. In other words, the
electron is endowed with a spin motion over and about the orbital motion. According to
the quantum theory, the spin of electron also should be quantized. Hence a new
quantum number called the spin quantum number (s) is introduced. Since the orbital
and spin motions are both quantized in magnitude and direction according to the idea
of spatial quantization, they are considered as quantized vectors. Hence the atom
model based on these quantized vectors is called the “vector atom model”.

According to the older theories, the electron was supposed to have only
orbital motion round the nucleus. Hence, only the orbital angular momentum and
orbital magnetic moment were considered. The spin endows the electron with a spin
angular momentum sh and a spin magnetic moment. Hence the total angular
momentum of an atom should be the vector sum of the orbital angular momentum and
spin angular momentum. Similarly, the total magnetic moment of an atom should be
the vector sum of the orbital and spin magnetic moments.
DIFFEENT QUANTUM NUMBERS
The following quantum numbers are required to completely
specify the state of an electron in an atom:

1) Principal Quantum Number (n) : It represents the shell as a whole. The range
of its value is n =1, 2, 3,4 …….. It determines the energy of the electron and the
size of its orbit.

2) Orbital Quantum Number (l): The range of its values is l = 0, 1, 2, 3…….(n-

1). It represents the sub-shell only. It can have n values. Thus, if n = 4, l can have
four values 0, 1, 2, 3. By convention, an electron for which l=0 is called s electron;
if l=1, p electron; l=2, d electron; l=3 f electron etc. It determines the shape of the
electron orbits and also the orbital angular momentum of the electron. The orbital
angular momentum pl of the electron is given by

h
pl  l
2
 3) Spin Quantum Number (s) : This has only one values, ½. The spin angular
momentum
h
ps  s where s = ½.
2
4) Total Angular Momentum Quantum Number (j): It has been found that
coupling occurs between the spin and orbital angular momenta of an electron which
has been described by another quantum number j called total angular quantum
number. It can have only two possible sets of values given by j  l  s with the
restriction that j is positive. The positive sign is taken when s is parallel to l and
minus sign when it is antiprallel as in fig (a) and (b). It determines the total angular
momentum of the electron i.e, the vector sum of orbital angular momentum and
spin angular momentum.

The spin and orbital angular

momenta couple vectorially as
in fig c.
5) Orbital Magnetic Quantum Number: The projection of
the orbital quantum number l on the magnetic field direction is
called the magnetic orbital quantum number ml. It takes
integral values ranging from –l to +l in steps of unity, there
are (2l+1) possible values of ml. For example, if l=3, the
permitted orientations of l is 7, for which ml = 3,2,1,0,-1,-2,-3
as shown in fig. l cannot be inclined to B at any other angle. It
defines the angular momentum parallel to an applied magnetic
field. It determines the orientation of the electron orbit in
space. This is known as ‘spatial quantization’

6) Spin Magnetic Quantum Number: This is the projection

of the spin vector s along the direction of the magnetic field.
The spin angular momentum (s) can assume only two possible
positions with respect to the magnetic field. It may be parallel
to it or antiparallel. ms can have only two values +1/2 or -1/2
as in Fig. it arises from quantization of the spin angular
momentum. It determines the spin orientation up or down.
7) Total Magnetic Quantum Number: This
is the projection of total angular momentum
vector j on the direction of the magnetic field.
Since we are dealing with a single electron, j
can have only odd half integral values. This
quantum number can have (2j+1) values
ranging from –j to +j with zero excluded. In
other words, its range is +j  mj  -j.

1 3 5
Or, m j   ,  ,  , .....  j.
2 2 2
 Values of n, l, j, mj Quantum Numbers
The values of different quantum numbers for electrons occupying
different shells and sub-shells etc are as under:

(a)Take n = 1. Then l = 0

j=l+s=0+½=½

and mj = +½, -½
Hence, the two 1s2 electrons have the following four quantum numbers each.

Electrons n l j mj
1st electron 1 0 1/2 +1/2
2nd electron 1 0 1/2 -1/2
 (b) Take n = 2. Here, l = 0, 1 and s = ½
(i) First take l = 0

j=l+s=0+½=½

and mj = +½, -½

Hence, the two 2s2 electrons have the following four quantum numbers each.

Electrons n l j mj
1st electron 2 0 1/2 +1/2
2nd electron 2 0 1/2 -1/2
 (ii) Now take l = 1 j = l + s = 1 + ½ = 3/2 (s=+1/2)

mj = -3/2, -½, +½, +3/2

When j = l + s = 1- ½ = ½ (s =-1/2)

mj = -½, +½
Hence, the six 2p6 electrons have the following values of their four quantum numbers.

SL No. of Electron n l j mj
1 2 1 3/2 -3/2
2 2 1 3/2 -1/2
3 2 1 3/2 +1/2
4 2 1 3/2 +3/2
5 2 1 ½ -1/2
6 2 1 1/2 +1/2
 Pauli’s Exclusion Principle
It states that no two electrons in an atom exist in the same quantum state. The four
quantum numbers n, l, j, and mj determine the state of an electron completely.
According to this principle, “No two electrons in an atom can have all the four
quantum numbers alike i.e. no two electrons can be described by an identical set
of quantum numbers.” They may have three quantum numbers alike but at least
one must be different.
Example
Consider the case of helium which has two electrons in its atom. These electrons
occupy K-shell (n=1) are designated as 1s2 electrons. Their four quantum
numbers are as follows:

n l j mj
1st electron 1 0 1/2 +1/2
2nd electron 1 0 1/2 -1/2
 Why is Electron’s spin ½?
In quantum mechanics, spin is an intrinsic property of all elementary particles.
Fermions, the particles that constitute ordinary matter, have half-integer spin. All
known elementary fermions have a spin of ½.

In Particle Physics, a fermion is a particle that floows Fermi-Dirac statistics. These

particles obey the Pauli’s exclusion principle.

Example
Quarks, Leptons, Hadrons (Baryons, mesons)
 Zeeman Effect
“Zeeman effect is a magneto-optical phenomenon discovered by Pieter
Zeeman in 1896”.

He won the Nobel prize in Physics along with Hendrick Lorentz

 A spectral line emitted by the excited atoms is split up into a doublet or triplet when
the emitting atoms are placed in a magnetic field. This effect of the splitting of a
spectral line under the action of a magnetic field is known as normal Zeeman Effect.

To produce Zeeman effect, the source of light such as a sodium lamp or a

mercury arc or gas discharge in a Geissler tube is placed between the poles of a
powerful electro-magnet (Fig. a). The light coming from the source is examined by
means of a spectroscope of high resolving power. In order to view the light parallel
to the magnetic field, a hold is drilled in one of the pole-pieces along the axis of
magnet.
 When no magnetic field is applied, the spectroscope is focused on one of the
lines in the spectrum of the source of light. When a magnetic field is applied, it is
observed:

Fig.5 Normal Zeeman effect (i) No field (ii) Perpendicular to the field
(iii) parallel to the field
1. That when the light is viewed in a direction perpendicular to the magnetic field, three
component lines are observed. One of the lines is in the same position as the original
line and the other two lines are in the two sides of the original line. The outer two
lines, when observed by means of a nicol prism as an analyzer, are polarized at right
angles to the undisplaced line. This effect is known as transverse Zeeman effect.

2. When the light is viewed in a direction parallel to the direction of the field, there is no
line in the position of the original line, only two outer lines are present. These lines
are found to be circularly polarized in opposite directions. This effect is known as
longitudinal Zeeman effect.
The normal Zeeman effect is explained on
Lorentz electron theory. Consider an
electron moving in a circular orbit of radius
r with a velocity v (as in Fig. 2)

The centripetal force is

mv 2
F Fig. 2
r
 If an external magnetic field is applied, an additional force acts which is
directed perpendicular to the direction of motion of the electron. This force is also
perpendicular to the direction of the magnetic field and is along the radius. When this
force acts inwards along the radius, the velocity of the electron increases. When this
force acts outwards along the radius, the velocity of the electron decreases. Suppose,
this force due to the magnetic field = F1 and let the velocity of the electron be increased
to v1 by application of the magnetic field.

Then, F1  Bev1 . Suppose, this force is directed towards the centre, total force along
the radius,
mv 2
 F  F1   Bev1
r
mv12
Total force 
r
2 2
mv mv
   Bev1
1
(i)
r r
But, v  r and v1  1r
where  and 1 are the respective angular velocities.

From equation (i)

m 12 r 2 m  2 r 2 or , m  2
r  m  2
r  Be  r
  Be 1r 1 1
r r
eB 1 e B1
or , 1   
2 2
or , (1   )(1   ) 
m m
eB 1 eB 1 eB
 (1   )   
m(1   ) m.21 2m
(1 + ) is approximately equal to 2 1.

eB
 1   
2m
 If 1 and  are the frequencies, then

eB
21  2 
2m
eB
1    (ii)
4 m
When the electron moves in the opposite direction, the magnetic field produces a force
in the opposite direction and the velocity decreases to v2. In that case

mv 2
Total force  F  F2   Bev2
r
2 2
mv mv
  2
 Bev2
r r
 But, v2  2 r and v  r

mr  2
mr 
2 2 2
  2
 Ber2
r r
eB 2
or , 2    
2 2

m
eB 2 eB
or , 2      (2 + ) = 2 2 approximately
m(2   ) 2m
eB eB
or , 2 2  2     2  
2m 4 m
This shows the two lines are displaced equally on the two sides of the original line.

eB eB
1  2  In general  
2 m 2 m
The quantity eB 2 m is known as normal Zeeman separation. Knowing the values
of  and B, e/m can be calculated. The value of e/m calculated from the measurements
of Zeeman effect is =1.757×1011 C/kg and it is in agreement with the value of e/m of
the electron obtained from Thomson’s experiment.

This experiment established that the electron in the atom is responsible for the emission
of spectral lines.