M. P. I.

ATOMIC STRUCTURES XI

Structure of Atom

Fundamental Particles:

From ancient times speculations were made by philosophers

about the exact nature of the matter. John Dalton (1766—1844), an English
scientist developed in the years 1803—1808 his famous atomic theory and
suggested that the matter was made of extremely small indivisible particles
called atoms. The word atom is a Greek word meaning indivisible i.e., an
ultimate particle which cannot be further subdivided. Dalton’s concept of the
atom had to be discarded at the end of the nineteenth century when several
experimental facts like the existence of the isotopes, disintegration of atoms
etc. came to light. During the last 100 years, scientists have made
contributions which helped in the development of modem theory of atomic
structure. The work of J.J. Thomson and Ernest Rutherford actually laid the
foundation of the modem picture of the atom.

It is now believed that the atom consists of several particles

called sub-atomic particles like electron, proton, neutron, positron, neutrino,
meson etc. Out of these particles the proton, electron and neutron are called
fundamental particles and are the building blocks of the atom.

Discovery of electron : Cathode Rays :

The nature and existence of electron was established by experiments on

conduction of electricity through gases in a discharge tube as shown in Fig. A
discharge tube consists of a glass tube about one inch diameter and perhaps
two feet long and has metal plates embedded at the ends and is provided with
an outlet through which the gas within the
tube can be progressively removed by
means of a vacuum pump. The metal
plates connected to a source of high voltage
are called electrodes. If the electrodes are

1
M. P. I. ATOMIC STRUCTURES XI

separated by as much as two feet and the pressure in the discharge tube is
decreased progressively by removing the gas, a series of spectacular events
occur. An electric current begins to flow and at the same time beautiful light
through the gas between the electrodes are seen. If the pressure is further
reduced to 1/1,000,000 of an atmosphere, the light disappears completely and
there is only a greenish glow emanating from the glass in the region of the
anode (positive electrode). If the gas pressure is reduced still further, the
current ceases to flew. By a series of ingenious experiments, conducted mainly
by the British physicist J.J. Thomson, it was shown that originating near the
cathode (negative electrode) was a swiftly moving stream of charged particles
which moved across the void between the two electrodes. These charged
particles were first called cathode rays because of their origin at the cathode;
later they were given the name electrons by Johnstone stoney.

Explanation of the Formation of Cathode Rays:

When a high potential difference is applied between two

electrodes, the atoms or molecules present in the gas in discharge tube
dissociate to produce electrons which constitute the cathode rays. Thus, for
example, if the discharge tube is filled with oxygen gas, the dissociation occurs
as :

 O   e
O
 O2  e 
O2 
O2 
 O2  e 

Properties of Cathode Rays

The properties of cathode rays were investigated by William

Crookes., J. Perrin., J.J. Thomson and others. Cathode rays possess the
following properties :

(i) Cathode rays travel in a straight line : Cathode rays cast shadow of the
solid (mica cross) placed in their path as shown in Fig. 2.2. Furthermore, as
2
M. P. I. ATOMIC STRUCTURES XI

the shadow falls on the walls opposite to the cathode, it confirms that cathode
rays travel from cathode to anode in straight line.

(ii) Cathode rays are made up of material particles : When a light paddle
wheel of mica mounted on an axle is placed in the path of the cathode rays as
shown in the Fig.. The wheel begins to rotate on being hit by the electrons. This
indicates that the cathode rays are made up of material particles.

(iii) Cathode rays carry negative charge : When an electric field is applied to
a stream of cathode rays. they are deflected towards the positive plate of the
electric field as shown in Fig. This indicates that cathode rays carry negative
charges.

3
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

(iv) Cathode rays are deflected

deflected by magnetic field : When the cathode rays
are made to pass through a strong magnetic field, the rays are deflected in a
specific direction. This further confirms that the cathode rays are negatively
charged.

Left hand rule for electron deviation of electron from velocity vector to
magnetic field & Right hand rule for protons deviation of protons from velocity
vector to magnetic field.

Direction of magnetic field in a magnet is from north to south.

(v) Cathode rays produce heating effect : When the cathode rays are allowed
to strike a thin platinum foil, it becomes red hot. This shows that cathode rays
produce heating effect.

(vi) Cathode rays produce X-rays

X : The cathode rays when strike a hard metal
surface (like tungsten, molybdenum, platinum,
platinum, copper etc.) produce X-rays.
X rays.

(vii) Cathode rays produce fluorescence:

fluorescence: The cathode rays produce faint
greenish tluorescence on striking the glass walls of the discharge tube or on

4
M. P. I. ATOMIC STRUCTURES XI

striking zinc suiphide or barium platinocyanide. The colour of fluorescence

light depends on the nature of substance.

(viii) Cathode rays ionise the gas through which they pass : Cathode rays, on
collision with the atoms of gases, can eject electrons from them, and thus
ionization of the gas occurs.

(ix) Cathode rays affect the photographic plates.

(x) Cathode rays penetrate through the thin foils of aluminium metal These
rays penetrate through the thin Al foil when placed in the path of cathode rays.

(xi) The charge to mass ratio (elm) for the negatively charged particles in the
cathode is independent of the nature of the gas taken in the discharge tube or
the nature of the cathode.

Determination of Charge and Mass of Electron:

(i) Determination of charge to mass ratio (elm) of electron (i.e., J.J.

Thomson experiment)

J.J. Thomson (1897) determined elm of electron by studying

the deflection of cathode rays under the simultaneous influence of electrical
and magnetic fields perpendicular to each other. The two fields were adjusted
in such a way that the cathode rays strike the fluorescent screen at the same
place as they do in the absence of either field. Thomson calculated the elm
ratio of the electrons from the magnitude of the applied magnetic and electric
fields.

5
M. P. I. ATOMIC STRUCTURES XI

The value of e/m was found to be 1. 76 108 coulombs/g (1. 76 1011
coulombs/Kg). Two important conclusions can be drawn from this observation.

(i) The electrons are universal constituent of all matter.

(ii) For an electron elm value is 176  108 coulomb s/g.

(ii) Determination of charge of the electron—Millikan’s oil drop method:

The first accurate determination of the charge of an electron (e) was made by
WA. Millikan (1909) by his famous oil drop experiment. The apparatus used by
him is shown in Fig. Small oil droplets are produced by an atorniser. The oil
drops enter the apparatus
through a small hole and
are allowed to fall under
gravitational force between
two charged metal plates.
The movement of a single
droplet is observed by a microscope. The space between two metal plates was
irradiated with X-rays. The X-rays ionised electrons from some of the air
molecules which in turn were caught by air droplets. As a result the oil droplet
becomes negatively charged by applying the electrical field on the droplet under
study, which balances the downward gravitational force, the droplet becomes
stationary. From the magnitude of the charge applied on the plate and the
mass of the droplet. the charge on the droplet was determined, which was
found to he 16  1019 coulombs.

6
M. P. I. ATOMIC STRUCTURES XI

Since this is the smallest charge carried by any charged

particle, it is referred to as one unh charge.

(iii) Determination of mass of electron: By knowing the value of elm ratio (by
J.J. Thomson’s experiment) and charge on the electron (by Millikan’s oil drop
method), it is possible to calculate the exact mass of a electron.

Thus, an electron is that subatomic fundamental particle

which carries one unit negative charge (16  10-19 coulombs) and has a mass
of 91  10-28 g.

(iv) Mass of electron relative to hydrogen atom :

1
The mass of electron (91  10-28 g) is approximately th
1837
the mass of a hydrogen atom as shown below. However , the mass of electron is
so small that for all practical purposes , its value is considered negligible.

Mass of 1 g atoms of hydrogen 1008 g

 Mass of 6021023 (Avogadro number ) atoms of hydrogen =

1008 g

1  008
Mass of one atom of hydrogen =  1  67 1024 g.
6  02 10 23

Mass of electron = 91  10-28 g

Mass of electron 9 11028 g 1

 24

Mass of oneatom of H 1 67 10 g 1837

7
M. P. I. ATOMIC STRUCTURES XI

1
or, Mass of an electron =  Mass of one atom of H.
1837

(v) Determination of Avogadro’s number, NA:

1 Faraday = 96500 coulombs = 965  104 coulomb.

Charge on one electron 1 602 10-19 coulomb

9  65 104 coulomb
Avogadro’s number (NA) =
1 602 1019 coulomb

= 602  1023 electrons

Electron as a Fundamental Particle

The fact that electron is a fundamental constituent of all

matter is further substantiated by the following observations

(i) Alkali metals emit electrons when exposed to ultraviolet light.

(ii) Many metal filaments emit electrons on strong heating.

(iii) Radioactive substances after spontaneous disintegration give out -rays

which are fast moving electrons.

(iv) All forms of matter give out electrons when they are exposed to X-rays.

Discovery of Proton : Anode Rays (or Canal Rays ):

Atom is known to be electrically neutral.

Since an atom contains negatively
charged electrons, it follows that some
positively charged particles must also be
present in it. The first direct roof for the

8
M. P. I. ATOMIC STRUCTURES XI

presence of positively charged particles in the atom was provided by the

discharge tube experiment conducted by Goldstein (1886) using perforated
cathode.

On passing the electric discharge at a low pressure he observed a new

type of rays streaming behind cathode. These are called anode rays or canal
rays or positive rays and produce green fluorescence on opposite wall (i.e.,
behind cathode) of discharge tube.

Explanation for the formation of anode rays:

The particles constituting anode rays are quite different from

the particles of cathode rays. First of all they are positively charged, and
secondly, they are massive particles, being of the same order of mass as the
atoms and molecules of which the gas is composed of. Could these particles be
what is left of the atom or molecule after an electron has been pulled out of the
atom ? This hypothesis is correct and is suggested by the fact that mass of
these particles varies with the gas used in the discharge tube. Thus, when a
high potential difference is applied between the electrodes in a discharge tube
tilled with a gas, say helium at a low pressure, there is produced a stream of
electrons moving toward the anode (positively charged electrode) and a stream
of positively charged particles or ions of atomic weight four moving in the
opposite direction i.e., towards cathode (negatively charged electrode). The
process may be represented as

He 
Electrical
Energy
 He   e 
Helium Helium Electron
atom ion

The same process would occur with the neon gas in the discharged tube,
but the canal rays will now be composed of positively charged neon atoms :

9
M. P. I. ATOMIC STRUCTURES XI

Ne 
Electrical
Energy
 Ne   e 
Neon Neon Electron
atom ion

Both helium and neon are monoatoinic molecules i.e., they are known to
consist of one atom per )lecule. In case of gas molecules consisting of two or
more atoms, such as nitrogen (N2), several reactions take place simultaneously.

In this case, in addition to electrons, there are formed positively charged

nitrogen molecule (N 2 ), and positively charged nitrogen atom (N+ ) by the

decomposition of nitrogen molecules. Neutral nitro are also produced but these
are not associated with the either electrode.

Rutherford pointed out that the lightest particle bearing unit positive
charge was produced from the hydrogen gas. Therefore, each particle is a
hydrogen atom devoid of an electron, thus bearing a unit positive charge. This
lightest positive ray particle was named as proton. Later on it was found that
the mass of positive particle produced from all gases is the simple multiple of
the mass of the proton. Thus, proton is a fundamental constituent of atoms
of all elements bearing unit positive charge and having mass almost equal
to that of a hydrogen atom.

Properties of Anode Rays

(i) Anode rays travel in straight lines.

(ii) Anode rays are made up of material particles.

(iii) Anode rays are deflected by electric field towards negatively charged plate.
This shows that anode rays consist of positively charged particles.

10
M. P. I. ATOMIC STRUCTURES XI

(iv) On applying a magnetic field in a direction perpendicular to the path of

anode rays, they get deflected in the direction expected for positive particles.
This shows that anode rays consist of positively charged particles.

(vi) Like cathode rays, they also cause heating effect.

(v) The e/in ratio of the particles in the anode rays depends upon the nature of
the gas taken in the discharge tube.

(vi) (e/m)proton = 9.58 x 104 C/g; e = 1.602 x 10-19 C & mp = 1.6725 x 10-24 g.

Discovery of Neutron:

After the discovery of electrons and protons, Rutherford

(1920) had predicted the existence of a neutral fundamental particle. In 1930,
Bethe and Becker reported from Germany that if certain light elements, like
beryllium, were exposed to alpha rays from the naturally radioactive polonium,
a very highly penetrating radiation was obtained. Similar results were obtained
by Irene Curie and F. Jolit (1932). Chadwick (1932) demonstrated that this
mysterious radiation was a stream of fast moving particles of about the same
mass as a proton but having no electric charge. Because of their electrical
neutrality, these particles were called neutron.

The lack of charge on the neutron is responsible for its great penetrating
power.

Protons of the same energy are stopped by a much thinner layer of

matter because of the interaction of their electric charges with the charges of
the nuclei and electrons in the matter they are traversing.

The lack of charge on the neutron is responsible for its great penetrating
power .

Protons of the same energy are stopped by a much thinner layer of

matter because of the interaction of their electric charges with the charges of

11
M. P. I. ATOMIC STRUCTURES XI

the nuclei and electrons in the matter they are traversing. The interaction of
beryllium and alpha particles can be written as :

Thus, a neutron is a sub-atomic fundamental particle which has a mass

1 6748  10-24 g (approximately 1 amu), almost equal to that of a proton or a
hydrogen atom but carrying no electrical charge. The elm value of a neutron is
thus zero.

Density of neutron = 1 x 1012 kg/cc.

It is unstable particle & its half life = 20 min : 10 n 11 p  01e  00 e  Antineutrino 

12
M. P. I. ATOMIC STRUCTURES XI

Other particles of atom:

1. Positron: C.D. anderson-1932: It bears a unit positive charge & its mass
= mass of electron. It merges with an electron & emits electromagnetic
0
radiation. It is denoted by 1 e.

2. Meson   : Yukawa 1935: m   m   273me , m 0  264 me .

3. Neutrino & Antineutrino  e  : Fermi & Pauling in 1927: These are

0
0

electroneutral particles.

4. Antiproton  p  : Serge 1956: It bears a unit negative charge & its masss
1
1

= mass of proton.

Note:

1. Mass of H-atom = 1837 x Mass of electron.

2. The mass of 1.1 x 1027 electron = one gram.
3. The mass of one mole of electron = 0.5583 mg.
4. One Faraday = Charge on 1 mole electron = 96500 C.
5. The mass of an electron at rest is called static electron mass = 9.1091 x
10-28 g.
Mass of e at rest
6. The mass of an electron in motion 
2
v 
1  e 
c
Ve = Velocity of electron, c = Velocity of light.
When ve = c, the mass of the electron in motion becomes infinity.
Therefore, mass of electron increases with increase in its velocity due to which
e/m ratio decreases.
7. Order of e/m ratio  n    p  e

13
M. P. I. ATOMIC STRUCTURES XI

Reduced mass of electron:

It has been assumed that the nucleus remains stationary except for
rotating on its own axis. This would be true if the mass of the nucleus were
infinite, but the ratio of mass of an electrom to the mass of the hydrogen
nucleus is 1/1837.

The nucleus actually oscillates slight about the centre of gravity, and to
aloow for this the mass of the electron m is replaced by the reduced mass.
1 1 1
 
 m1 m2

The reduced mass is always less than or equal to the mass of each body.
1 1 1 mm
  m1 ,   m2 , and has the reciprocal additive property:    1 2
 m1 m2 m1  m2

Discovery of nucleus: Ernst Rutherford 1911:

A beam of alpha-particles directed against a thin foil of about 4 x 10-4 cm

thickness of gold, silver copper etc. the foil was surrounded by a circular
fluorescent ZnS screen whenever an alpha-particle struck the screen, it
produced a flash of light.

14
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

Observation:

i. Greater the angle of scattering, lesser is the number of alpha-particles

alpha particles
deflected.

ii. Nearly 99% alpha-particles

alpha particles went straight without suffering any
deflectrion.
iii. A few of them got deflected through small angles.
iv. A very small numbers of alpha-particles
alpha particles rebounded after colloiding with
the gold foil i.e. about 1/20000.
1/20000.

Inferences:

i. Most of the part of an atom is vacant.

vacant
ii. Whole of the mass of an atom is confined to its nucleus.
iii. The radius of the atomic nucleus is in order of 10 15 m  10 13 cm  Fermi .
1
rn  1.33 A 3 F

iv. The radius of an atom is in order of 10 10 m  10 8 cm  A0 .

v. Atomic radius = 105 x Atomic nucleus.

vi. Atomic volume  1015 x Volume of nucleus.

vii. Nuclear density  2.4 x1017 kg / m3

15
M. P. I. ATOMIC STRUCTURES XI

Moseley’s Experiment for Atomic numbers or Nuclear Charge:

Moseley studies on the characteristic X-ray spectra for various target elements
using the X-ray diffraction technique.

When a target material (anticathode) was placed in the path of cathode rays. X-


rays Wavelengthbetween     0.1  20 A0  were produced.

Observation:

It was observed that the wavelength of X-rays were the characteristic of

each element. The characteristic X-rays spectrum consist of discrete spectral
lines which can be grouped into K-series, L-series, M-series etc.

Analysis of the result:

It was suggested by Moseley that the fast-moving cathode rays were able
to remove electrons from the inner-orbits (i.e. K, L, M etc) of an atom of anti
cathode due to collision. This creates vacancy in the innershells. Under the
influence of nuclear charges electrons from higher shells fall in those shells.

He found that the K freuquency line in the X-ray spectra from a particular

target element is varied smoothly with that element’s atomic number Z.

Moseley law:

Moseley’s law is an empirical law concerning the characteristic X-rays

that are emitted by atoms. “The law that the square-root of the frequency of an

16
M. P. I. ATOMIC STRUCTURES XI

X-ray spectral line belonging to a particular series is proportional to the

difference between the atomic number and a constant which depends only on
the sereis”.

c
v  Z, v v  a Z  b,


a  Pr oportionaly cons tan t & b  Screening cons tan t

Importance of Moseley experiment:

i. Atomic number is more important than Atomic weight as it is equals to

charge of nucleus.
ii. Difference between Ni, Co, Te & I etc, is explained when periodic table
constructed with atomic number.
iii. Moseley predicted the existence of elements with atomic number 43, 61,
72 & 75. Thus X-ray spectrum analysis new elements can be discovered.

Atomic models:

1. Thomson atomic model/ Plum-Pudding model/ Watermelon model

(1898):
i. Thomson put forward the ist model of an atom on the basis of the
information obtained from the experiments on cathode & anode rays.
ii. Atom is a very minute, spherical, electroneutral particle that consists of
positively & negatively charged matter.
17
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

iii. The positively charged matter is uniformly distributed in the atom &
negatively charged electrons are embedded in it.

Limitation of Thomson’s
Thomson’s atomic model:

 Thomson’s atomic model failed to explain how the positive charge holds
on the electrons inside the atom. It also failed to explain an atom’s stability.

 The theory did not mention anything about the nucleus of an atom.

 It was unable to explain the scattering experiment of Rutherford.

2. Rutherford Atomic Model:

Rutherford’s conducted an experiment by bombarding
bombarding a thin sheet of
gold with α-particles
α particles and then studied the trajectory of these particles after
their interaction with the gold foil.
Rutherford, in his experiment, directed high energy streams of α-
α
particles from a radioactive source at a thin sheet (100
(100 nm thickness) of gold.
In order to study the deflection caused to the α-particles,
α particles, he placed a
fluorescent zinc sulphide screen around the thin gold foil. Rutherford made
certain observations that contradicted Thomson’s atomic model.
model

Observations of Rutherford’s Alpha Scattering Experiment

The observations made by Rutherford led him to conclude that:

1. A major fraction of the α-particles

α particles bombarded towards the gold sheet
passed through it without any deflection, and hence most of the space in an
atom is empty.
empty

18
M. P. I. ATOMIC STRUCTURES XI

2. Some of the α-particles were deflected by the gold sheet by very small
angles, and hence the positive charge in an atom is not uniformly
distributed. The positive charge in an atom is concentrated in a very small
volume.
3. Very few of the α-particles were deflected back, that is only a few α-
particles had nearly 1800 angle of deflection. So the volume occupied by the
positively charged particles in an atom is very small as compared to the
total volume of an atom.

Based on the above observations and conclusions, Rutherford proposed

the atomic structure of elements. According to the Rutherford atomic model:

1. The positively charged particles and most of the mass of an atom was
concentrated in an extremely small volume. He called this region of the atom as
a nucleus.
2. Rutherford model proposed that the negatively charged electrons
surround the nucleus of an atom. He also claimed that the electrons
surrounding the nucleus revolve around it with very high speed in circular
paths. He named these circular paths as orbits.
3. Electrons being negatively charged and nucleus being a densely
concentrated mass of positively charged particles are held together by a strong
electrostatic force of attraction.

Limitations of Rutherford Atomic Model

Although the Rutherford atomic model was based on

experimental observations it failed to explain certain things.

 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

19
M. P. I. ATOMIC STRUCTURES XI

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 the Rutherford model, an electron would
collapse in the nucleus in less than 10-8 seconds. So Rutherford model
was not in accordance with Maxwell’s theory and could not explain the
stability of an atom.

 One of the drawbacks of the Rutherford model was also that he did not
say anything about the arrangement of electrons in an atom which made
his theory incomplete.

 Although the early atomic models were inaccurate and failed to explain
certain experimental results, they were the base for future developments in
the world of quantum mechanics.

Wave:

A wave is a periodic disturbance in which energy is transferred from one

point to another without any transfer of matter between these points.

Electromagnetic radiations:

Electromagnetic radiation is a form of energy that is produced by

oscillating electric and magnetic disturbance, or by the movement of electrically
charged particles traveling through a vacuum or matter. The electric and
magnetic fields come at right angles to each other and combined wave moves
perpendicular to both magnetic and electric oscillating fields thus the
disturbance. Electron radiation is released as photons, which are bundles of
light energy that travel at the speed of light as quantized harmonic waves. This
energy is then grouped into categories based on its wavelength into the
electromagnetic spectrum. These electric and magnetic waves travel

20
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

perpendicular to each other and have certain characteristics, including

amplitude, wavelength, and frequency.
frequency.

General Properties of all electromagnetic radiation:

1. Electromagnetic radiation can travel through empty space. Most other

types of waves must travel through some sort of substance. For example,
sound waves need either a gas, solid, or liquid to pass through in order to be
heard.

2. The speed of light is always a constant. (Speed of light : 2.99792458 x

108 m s-1)

3. Wavelengths are measured between the distances of either crests or

troughs. It is usually characterized by the Greek symbol λ.
Waves and their Characteristics

21
M. P. I. ATOMIC STRUCTURES XI

Amplitude

Amplitude is the distance from the maximum vertical displacement of the

wave to the middle of the wave. This measures the magnitude of oscillation of a
particular wave. In short, the amplitude is basically the height of the wave.
Larger amplitude means higher energy and lower amplitude means lower
energy. Amplitude is important because it tells you the intensity or brightness
of a wave in comparison with other waves.

Wavelength

Wavelength (λ) is the distance of one full cycle of the oscillation. Longer
wavelength waves such as radio waves carry low energy; this is why we can
listen to the radio without any harmful consequences. Shorter wavelength
waves such as x-rays carry higher energy that can be hazardous to our health.
Consequently lead aprons are worn to protect our bodies from harmful
radiation when we undergo x-rays. This wavelength frequently relationship is
characterized by:

c=λν (1)

Where

 c is the speed of light,

 λ is wavelength, and
 ν is frequency.

Shorter wavelength means greater frequency, and greater frequency

means higher energy. Wavelengths are important in that they tell one what
type of wave one is dealing with.

22
M. P. I. ATOMIC STRUCTURES XI

Note: Wavelength tells you the type of light and Amplitude tells you about the
intensity of the light.

Frequency

Frequency is defined as the number of cycles per second, and is

expressed as sec-1 or Hertz (Hz). Frequency is directly proportional to energy
and can be express as:

E=hν (2)

Where

 E is energy,

 h is Planck's constant, (h= 6.62607 x 10-34 J), and

 νν is frequency.

Period

Period (T) is the amount of time a wave takes to travel one wavelength; it
is measured in seconds (s).

Velocity

The velocity of wave in general is expressed as:

velocity=λν (3)

23
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

For Electromagnetic wave, the velocity in vacuum is 2.99×108

m/s or 186,282 miles/second.

Electromagnetic spectrum

24
M. P. I. ATOMIC STRUCTURES XI

Radiation Types

Radio Waves are approximately 103 m in wavelength. As the name

implies, radio waves are transmitted by radio broadcasts, TV broadcasts, and
even cell phones. Radio waves have the lowest energy levels. Radio waves are
used in remote sensing, where hydrogen gas in space releases radio energy
with a low frequency and is collected as radio waves. They are also used in
radar systems, where they release radio energy and collect the bounced energy
back. Especially useful in weather, radar systems are used to can illustrate
maps of the surface of the Earth and predict weather patterns since radio
energy easily breaks through the atmosphere. ;

Microwaves can be used to broadcast information through space, as well

as warm food. They are also used in remote sensing in which microwaves are
released and bounced back to collect information on their reflections.

Microwaves can be measured in centimeters. They are good for

transmitting information because the energy can go through substances such
as clouds and light rain. Short microwaves are sometimes used in Doppler
radars to predict weather forecasts.

Infrared radiation can be released as heat or thermal energy. It can also

be bounced back, which is called near infrared because of its similarities with

25
M. P. I. ATOMIC STRUCTURES XI

visible light energy. Infrared Radiation is most commonly used in remote

sensing as infrared sensors collect thermal energy, providing us with weather
conditions.

Visible Light is the only part of the electromagnetic spectrum that

humans can see with an unaided eye. This part of the spectrum includes a
range of different colors that all represent a particular wavelength. Rainbows
are formed in this way; light passes through matter in which it is absorbed or
reflected based on its wavelength. Thus, some colors are reflected more than
other, leading to the creation of a rainbow.

Ultraviolet: Ultraviolet radiation is emitted by the Sun and are the

reason skin tans and burns. "Hot" objects in space emit UV radiation as well.

X-ray: A dentist uses X-rays to image your teeth, and airport security
uses them to see through your bag. Hot gases in the Universe also emit X-rays.

Gamma ray: Doctors use gamma-ray imaging to see inside your body.
The biggest gamma-ray generator of all is the Universe.

26
M. P. I. ATOMIC STRUCTURES XI

Quantum Mechanical Model of Atom (Quantum Mechanics):

Quantum mechanics was developed by Ervin Schrodinger in 1926. He

described the behavior of electrons around the nucleus by a mathematical
equation, known as Schrodinger wave equation in 3-D space.

 2  2  2 8 2 m
   2  E  V   0
dx 2 dy 2 dz 2 h

   E ;
H   Total energy operator called Hemilton operator
H

T  V    E; T  K .E. operator , V  P.E. operator

Ze 2
The potential energy at a distance r is given by V  
4 0 r

 2  2  2 8 2 m  Ze 2 
    E    0
dx 2 dy 2 dz 2 h2  4 0 r 

8 2 m  Ze 2 
2   E    0
h2  4 0 r 

Exact solution of the equation is rather difficult. The spherical symmetry

of the system suggests that it would be convenient to use the polar coordinates
r, θ and ϕ. ‘r’ is the distance of the electron from the nucleus, θ is the angle Poz
(with the z axis P is the position of electron) and ϕ is the angle Mox which the
projection r on the xy plane makes with the x-axis. The Cartesian and Polar
coordinates are related by the expression:

x  r sin  cos 
y  r sin  sin 
z  r cos 
r 2  x2  y2  z 2

27
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

The wave function Ψ = Amplitude of the wave

Significance of wave function:

The Max Born interpretation of Ψ is based on an analogy with the wave theory
of light in which the square of the amplitude of an electromagnetic wave is
interpreted as the intensity and therefore, in quantum terms, as the number of
photons present. The Born interpretation is that the square of the wave
function. i.e. Ψ2 is proportional to the finding the particle at each point in
space.

If Ψ2 is high, the probability of finding the particle is high, and

a if Ψ2 is
low, the probability is low.

The mathematical form of the wave function for an electron in an atom is

obtained by solving the Schrodinger wave equation. The solution Ψ for the
electron, often containing an imaginary quantity, may be expressed as

Ψ = a + ib then Ψ* = a – ib and

ΨΨ* = (a + ib) (a - ib) = a2 + b2 ; which is a real quantity (i2 = -1)

If Ψ does not involve imaginary quantity Ψ = Ψ* and ΨΨ* = Ψ2

28
M. P. I. ATOMIC STRUCTURES XI

In case of three dimensions, the wave function is normalized if

  
  
  
 * dx dy dz  1


  *d  1 Where d  dxdydz 


If Ψ2 is a probability then Ψ must have the following properties:

(a) Ψ must vary continuously. It can be +ve, -ve, zero.

(b) Ψ = 0 is not acceptable because probability can not be zero every where.
(c) Ψ should be single valued function that is it can have only one value at
every point.
(d) Ψ has a continuous slope.
(e) Ψ must be finite.
(f) Ψ is not measurable.
(g) Ψ2 is a measurable quantity
(h) Ψ2 = Probability density = probability/volume
(i) Probability = Ψ2 x volume

Important features of quantum mechanical model:

(a) The energy of an electron in an atom is quantized.

(b) The existence of quantized electronic states is adirect consequence of the
wave properties of electrons.
(c) The exact position & velocity of an electron in an atom can not be
determined simultaneously, hence we consider the probability of finding the
electron at different positions in the atom.
(d) The wave function are the mathematical function of the coordinates of
the electron associated with each energy state, are called atomic orbitals or
hydrogenic orbitals.
(e) In each orbital, the electron has a definite energy

29
M. P. I. ATOMIC STRUCTURES XI

(f) An orbital can not contain more than two electrons.

(g) The wave function Ψ is the storehouse of all information about an
electron in an atom.
(h) The probability of finding an electron at a point within an atom is
proportional to the square of the orbital wave function (Ψ2) at that point Ψ2 is
known as the probability density and is always positive.
(i) Probability of finding an electron is not 100% in an orbital.
(j) The probability of finding the electron summed over all space must be
unity. i.e. the wave function must be normalized.

To solve this equation, we apply the method of separation to break down

the wave function Ψ into three parts, each of which is a function of only a
single variable. It is possible to express Ψ as a product of three function
 r ,  and   which depend on r, θ and ϕ respectively. Thus:

  r , ,    r . . 

or

  r , ,   R r  .  . 

Where R is a function of r only (i.e. the mathematical expression R

involves only the distance r of the electron from the nucleus), and besides
depending on r, involves two constant n and l. hence the function R
represented as:

 r  R r     n ,l 

 r  R r   Radial wave function

30
M. P. I. ATOMIC STRUCTURES XI

Where  is a function of angle θ only (i.e. the mathematical expression

of  involves the angle θ), and besides depending on θ, involves two constant l
and m where m represents the magnitude of the constant m. hence the

function  represented as:

       l ,m 

     Zenith (angular) wave function

Where  is a function of the angle ϕ only (i.e. mathematical expression of

 involves the angle ϕ), and besides depending on ϕ, involves two constant m.
hence the function ϕ represented as:

       m

      Azimuthal (angular) wave function

Where Y ,   Angular wave function

The wave function can then be separated into three separate equations
each involving one variable r, θ and ϕ respectively.

Quantum numbers:

The wave equation provides more than one solution of Ψ, i.e. more than
one function satisfies this equation. Each wave function constitutes what is
known as an orbital in the atom. The function, besides depending upon the
corresponding independent coordinates, also depend on the three integral
numbers designated as n, l and m respectively. These numbers which
automatically emerge as we solve the Schrodinger equation, are known as
quantum numbers, since they represent the quantization of definite physical

31
M. P. I. ATOMIC STRUCTURES XI

properties about the electron in the atom. Principal, azimuthal and spin
quantum numbers are the solutions of Schrodinger wave equation.

1. Principal quantum number (n) :

The quantum number n known as principal quantum number, can have

only 1, 2, 3, ……upto ∞. In one-electron system (such as H, He+, Li2+ etc), the
energy & distance of the electron is given by the value of the principal quantum
number only and may be given by the expression:

2 2 mk 2 Z 2e4 n2 h2
En  rn 
n2 h2 4 2 mkZe 2

The energy of electron increases with increase in the value of n. this

implies that the electron becomes less tightly attached to the nucleus. It is zero
energy when n is infinity, i.e. when the electron is not bound to the nucleus.

In a multi electron atom, the energy of the shell, besides depending upon
the quantum number n, is also determined by the quantum number l.

The varius permitted combination of n and l are possible. For each

permitted combination of n and l. the R equation provides a distinct solution of
R. these are represented by R1,0, R2,0, R2,1, R3,0, and so on where the first
subscript represents the principal quantum number n and the next one
represents second quantum number l (Azimuthal quantum number). Thus, the
function R1,0 constitutes the equation for the radial part of the wave function
for 1s orbital, R2,0 for 2s orbital, R2,1 for 2p orbital, R3,2 for 3d orbital and so on.

2. Azimuthal quantum number (l):

The quantum number represents the quantized values of angular

momentum of the electron in an orbital and is given by the expression:

32
M. P. I. ATOMIC STRUCTURES XI

 h 
L  l  l  1   h  6.625 x1034 J s
 2 

Mag . moment   l  l  1 B.M .

The quantum number l, known as azimuthal or subsidiary quantum

number, can have only integral values including zero. The maximum permitted
value of l is restricted by principal quantum number and is equal to (n-1)

l = 0, 1, 2, ……., (n-1)

The maximum value of l is thus (n-1). With each value of l, a letter has
become associated, each corresponding to a different sublevel, or set of atomic
orbitals:

l= 0, 1, 2, 3, …….., (n-1)

s, p, d, f………

For a given value of n, the total allowed values of l are equal to n; these
represent various subshells within the principal quantum shell. For a one
electron system (such as H, He+, Li2+ etc), the various subshells within a
principal shell are degenerate, i.e. all have the same energy. For multi-electron
system, the energies of varius subshells within a principal shell increase with
increase in the value of l.

3. Magnetic quantum number (m):

The magnetic quantum number, m designates the spatial orientation of a

single atomic orbital. The value of m for a given value of l can be from
–l…..0…..+l.

ml  l cos  ; 0 0
   1800  ; i.e. m  2l  1

33
M. P. I. ATOMIC STRUCTURES XI

When an electron is put in a magnetic field, the angular momentum (it is

vector quantity has magnitude as well as direction) of the electron takes only
some specific orientations with respect to the z-axis such that the component
of the angular momentum also has quantized values and is given by the
 h 
expression: Lz  m   ; where m = Magnetic quantum number.
 2 

The +ve value of of m describes orbital angular momentum of the

electron are the direction of magnetic field & -ve value of m describes orbital
angular momentum of the electron are in the direction opposite of magnetic
field.

4. Spin quantum number (s):

Electron spin is not acceptable in wave mechanics as wave mechanics

does not recognize the electron as a particle. Dirac developed a wave equation
and solution of that equation provided the spin quantum number.

An electron spin around its own axis, and thus spinning produces
angular momentum whose value is given by the expression:

h
 s  s  s  1 Where s = Spin quantum number & has a value of ½.
2

The z-component of this angular momentum is also quantized and is

given by the expression:

 h 
Lz  s   Where “s” is either + ½ (Clockwise spin) or – ½
 2 
(Anticlockwise spin). The spin of the electron is genrally represented by an
upward arrow ↑ (+ ½ ) or a downward arrow ↓ (- ½ ).

34
M. P. I. ATOMIC STRUCTURES XI

Thus, an electron in an atom is completely characterized by four

quantum numbers n, l, m and s.

Summary of relationship between main energy levels & sublevels:

Energy level Allowed l values Sublevels designations

n
1 0 1s
2 0, 1 2s, 2p
3 0, 1, 2 3s, 3p, 3d
4 0, 1, 2, 3 4s, 4p, 4d, 4f
5 0, 1, 2, 3, 4 5s, 5p, 5d, 5f, 5g
6 0, 1, 2, 3, 4, 5 6s, 6p, 6d, 6f, 6g, 6h
7 0, 1, 2, 3, 4, 5, 6 7s,7p, 7d, 7f, 7g, 7h, 7i

Number of equivalent orbitals in sublevels:

Types of Value of Allowed value of m No. of equivalent

subshell l orbitals in sublevel
s 0 0 1
p 1 -1, 0, +1 3
d 2 -2, -1, 0, +1, +2 5
f 3 -3, -2, -1, 0, +1, +2, +3 7
g 4 +4, -3, -2, -1, 0, +1, +2, 9
+3, +4

35
M. P. I. ATOMIC STRUCTURES XI

The mathematical forms of the wave function that are solutions of the
wave equation for hydrogen like species are given as:

36
M. P. I. ATOMIC STRUCTURES XI

Features of wave functions:

1. All the radial wave functions decay exponentlly with increase in r ; the
decay is slower for n = 2 and 3 than for n =1. Thus the likelihood of the
electron being further away from the nucleus increases with increase in n.
2. For n > 1, The wave function is zero in certain regions which are known
as nodes. As a general rule there are (n - 1) nodes in an s-atomic wave
function.
3. Node: The wave function is zero in certain region or where the probability
of finding of an electron is zero.
4. Radial nodes: Spherical region (surface) where the value of radial wave
function is zero, i.e. R r     r   0 . Total numbers of radial nodes :  n  l  1

5. Angular nodes: Generally rectangular region (surface) where the value of

radial wave function is zero, i.e.   ,   0 or    0 &     0 .

Total numbers of angular nodes :  l 

Orbitals Vale Value Radial nodes Angular Total

of n of l  n  l  1 nodes  l  nodes
 n  1
1s 1 0 0 0 0
2s 2 0 1 0 1
3s 3 0 2 0 2
2px 2 1 0 1 1
3py 3 1 1 1 2
5d 5 2 2 2 4

37
M. P. I. ATOMIC STRUCTURES XI

Radial nodes:  n  l  1

Anular nodes:  l 

1. S-orbitals: No such plane is present where the value of   ,   0 , hence

s-orbital is independent of angular wave function. Therefore number of nodal

plane for s orbital is equal to zero.
2. P-orbitals: Each P-orbitals have one such plane where the value of
  ,   0 , Therefore number of nodal plane for p-orbitals is equal to one.

3. d-orbitals: Each d-orbitals have two such plane where the value of
  ,   0 , Therefore number of nodal plane for d-orbitals is equal to two.

38
M. P. I. ATOMIC STRUCTURES XI

d z 2  orbital the two nodes two cones where the value of   ,   0 .

4. all f-orbitals have three angular nodes. These are combinations of nodal
planes and cones, depending on the particular f-orbitals.

39
M. P. I. ATOMIC STRUCTURES XI

40
M. P. I. ATOMIC STRUCTURES XI

First few radial wave functions for hydrogen (Z=1), R(r), n,l

Plots of radial wave functions R r  vs r

1. S-orbitlas: Consider the radial wave functions for 1s, 2s and 3s orbitals:

32
 z 
1s wave function R1,0  2   e  zr a0
 a0 

32
1  z   zr   zr 2 a0
2s wave function R 2,0     2  e
2 2  a0   a0 

41
M. P. I. ATOMIC STRUCTURES XI

1  z 
32
 18 zr  zr    zr 3a0
2

3s wave function R3,0     27   2   e

81 3  a0   a0  a0  


Since the exponential factor for 2s-function has the term  zr 2a0 as

compared to  zr a0 for the 1s-function, as r increases the 2s-function decreases

in amplitude more slowly than the 1s-function. This is why 2s-electron tends to
stay away from the nucleus and has higher energy than that of 1s-electron.

 zr 
Besides this factor  2   introduces a new feature in the function for
 a0 

2s-orbital. Depending upon the value of  zr a0  , the wave function can be

positive, zero or negative. Thus,

For small value of r,  zr a0   2 , and the wave function is positive;

For large value of r,  zr a0   2 , and the wave function is negative; and for

 zr 
r  2a0 z , zr a0  2 and the factor  2   is zero, the wave function R r   0 .
 a0 

Thus, at R r   0 , a node appears for the 2s function  for r  2a0 z  .

Similarly, for 3s orbital the exponential factor  3 zr 3a0  , which means

that the wave function decreases even more slowly with increasing r. thus, the
3s-orbital is still further away from the nucleus.

2. P-orbitals: Consider the radial wave functions for 2p and 3p orbitals:

32
1 Z Zr  Zr 2 a0
2p-wave function   2,1    e
2 6  a0  a0

42
M. P. I. ATOMIC STRUCTURES XI
32
4 Z  Zr  Zr Zr 3a0
3p-wave function  3,1    6  e
81 6  a0   a0  a0

Inspection of the radial wave functions for the 2p-orbitals reveals that no
nodes exist at finite values of r. The function R(r) is zero at r = 0 as compared to
Zr
the 2s-wave function which is zero at r  . Thus for 2p-wave functions a
a0

node exists at r  0 . This is a significant difference. Analogous plots of R, and

R2 can be drawn for the 2p, 3p and 3d orbital electrons.

Plots of radial probability density i.e. R2r  vs r

1. S-orbitals: Although R r  is a function which is not directly related to any

experimentally measurable quantity, the function R2r  is proportional to

electron density and therefore has considerable physical significance. R2r  is

plotted verses r for 1s, 2s, and 3s orbitals.

Note that R2r  has maximum value at the nucleus and that nodes

appear for  n  1 . Another important point to note that R2r  is never negative; a

negative value of electron density is physically meaningless.

43
M. P. I. ATOMIC STRUCTURES
ST UCTURES XI

One important feature of any s-electron

s electron distribution function that is not
from R r  vs  r  and R2r  vs r is that the distribution is independent of θ and ϕ;; it

is spherically symmetric.
symmetric

2. wavefunction a node exists at  r  0  . This is a

P orbitals: For 2p-wavefunction
P-orbitals:

significant difference. Analogous plots of R, and R2 can be drawn for the 2p, 3p
and 3d orbital electrons.

Radial probability distribution curves R2r  dV vs r or R2r  4 2r 2dr vs r :

Since we are mainly interested in the probability of finding electrons at

various point in space, we should deal with the square of the radial functions
than with the functions themselves. It is convenient to consider the atom to be
composed of “layers” much like an onion and to examine the probability of
finding the electron in the “layer” which extends from r to (r+dr). the volume of
thin shell may be considered to be dV. Now the volume of the shell is
calculated as follows:

4 4
dV    r  dr    r 3
3
r
r+dr
3 3 dr

4 4 r
dV    r 3  3r 2 dr  3rdr 2  dr 3    r 3
3 3

44
M. P. I. ATOMIC STRUCTURES XI

4
dV    r 3  3r 2dr  3rdr 2  dr 3  r 3 
3

4
dV    3r 2 dr  3rdr 2  dr 3 
3

Because dr is very small, 3rdr 2 and dr 3 are

extremely small and can be ignored. Hence,

4
dV    3r 2 dr 
3

dV  4 r 2 dr

The main features of the radial probability distribution function are:

(a) At r  0, 4 r 2 R 2  0 ; hence the value at the nucleus must be zero.

(b) At large value of r , R approaches zero rapidly and hence 4 r 2 R 2 must

approaches zero.
(c) In between r and R both have finite values, hence there is maximumin the

plot of probability  4 r 2 R 2  as a function of r . This maximum occurs at r  a0 .

The value of Bohr radius.

45
M. P. I. ATOMIC STRUCTURES XI

Most probable distance of electron from nucleus rm. p . : Distance at which

probability of finding of electron is maximum or the distance at which 4 r 2 R 2 is

maximum.

d
If r  rm. p. 
dr
 4 r 2 R 2   0

Average distance of electron from nucleus ravg : The average distance of

the electron from the nucleus is found weighting each possible distance with
the probability that the electron will be found at that distance.

For the same orbit:

ravg : nf  nd  np  ns & rm. p . : ns.np  nd  nf

1
Penitration effect  : ns  np  nd  nf
ravg

Energy of orbitals:

1. Energy of orbitals for single electron species depends only on “n”

 Energy :1s  2 s  2 p  3s  3 p  3d  4 s  4 p  4d  4 f  ...

2. Energy of orbitals for multi electron species depends on  n  l 

46
M. P. I. ATOMIC STRUCTURES XI

 Energy :1s  2 s  2 p  3s  3 p  4 s  3d  4 p  5s  4d  5 p  ....

Orbitals of the same subshell are called degenerate orbitals.

In the presence of external magnetic or electric field orbitals of same sub-

shell or electrons in the same orbital are not degenerate orbitals.

Angular wave function:

47
M. P. I. ATOMIC STRUCTURES XI

Plots of angular wave function   ,  vs  , :

1. S-orbitals: The angular wave function is independent of θ and ϕ and has

a constant value. Thus an s-orbital is spherically symmetrical.

2. P-orbital: The angular part of the Pz wave function is independent of ϕ.

The Px and Py orbitals are similar, but are oriented along the x and y axes,
respectively.

There is important feature of the p-orbitals;

If we consider the Pz orbitals,

 a  If 900    2700 then cos  ve

 b  If 900    2700 then cos  Zero

 c  If 900    2700 then cos  ve

Thus one lobe of the orbital has a different sign from that of the other.
This is also true for Px and Py orbitals.

48
M. P. I. ATOMIC STRUCTURES XI

The plots of the angular wave function against  and  give three
dimensional surfaces for each l and m value and are called orbitals. These plots
give the definite geometry of orbitals.

3. d-orbitals:

Shapes of orbitals or plots of  2 , 

1. s-orbitals: For s-orbitals, the values of quantum numbers l  0 and m  0 ,

for these values, the functions  and  are found to be independent of angles
 and  , respectively. Each of these two functions is equal to a constant term,

hence, for such orbitals  2n,0,0  R2n,0

As we know that the probability of finding the electron is maximum at

r  0 and it decreases exponentially with r.

Three dimentional plots of  2 vs r can be conveniently shown either by

plotting dot-population picture (the electron cloud density pattern) or by
drawing a boundry surface (or equal probability contour) plots. We can draw
contours within which there exists a total 90% probability.

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M. P. I. ATOMIC STRUCTURES XI

2. p, d and f-orbitals: On squaring of   ,  makes the plots more elongated.

Note:

1. for pz , d z 2 & f z3 orbitals the value of ‘m’ is zero.

2. Quantum numbers n, l & m are interrelated.

3. Spin quantum is independent of n, l & m quantum numbers.
4. An orbital can accommodate Maximum of 2 electrons with opposite spin.
5. The maximum capacity of s,p,d and f-sub-shells are 2,6,10 and 14
electrons respectively.

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M. P. I. ATOMIC STRUCTURES XI

Electronic configuration:

1. Aufbau Principle:

In multi electron atoms, the energy of electron depends on both principal

quantum number and azimuthal quantum number. i.e. n  l  value .

a. In building up an atom, electrons enter in to various orbitals in the

increasing order of their energy. i.e. the orbital of lowest energy is filled first.
b. The relative energy of various orbitals can be obtained by using  n  l  rule
c. The energy value of orbital increases as its  n  l  value increases.

Exa:  n  l  value of 1s-orbital is 1  0  1 and that of 2s-orbital is

 2  0  2  , hence energy of 1s  2 s

d. If two orbitals have same value of  n  l  , the orbital having lower n value

is first filled. Exa:  n  l  value of 2p-orbital is  2  1  3 and that of 3s-orbital is

 3  0  3 . Hence energy of 2 p  3s .

e. The energy of 4 f  5d  6 p  7 s but all are having n  l  7 .

f. The energy of orbitals in multi electron atom is:
1s  2 s  2 p  3s  3 p  4 s  3d  4 p 
5 s  4 d  5 p  6 s  4 f  5d  6 p  7 s  5 f  6 d  7 p
g. The energy of electron in hydrogen atom is determine only by principal
quantum number (n).

1s  2 s  2 p  3s  3 p  3d  4 s  4 p  4d  4 f 
5 s  5 p  5d  5 f  6 s  6 p  6 d  6 f  7 s  7 p

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M. P. I. ATOMIC STRUCTURES XI

2. Pauli’s Exclusion Principle:

a. No two electron in an atom can have the same value for all the four
quantum numbers.
b. Two electrons in a given orbital have same values of n, l & m , but differ in
their spin quantum number.
c. An orbital can not accommodate more than two electrons.
d. The capacity of S, P, d and f sub-shells are 2, 6, 10 and 14 electrons
respectively. i.e.  4l  2 

e. The capacity of K, L, M and N…..shells is 2, 8, 18 and 32…….electrons

respectively. i.e.2n 2

3. Hund’s rule of maximum multiplicity:

a. Orbitals of a given sub-level (denerate orbitals) should be half filled

before electron pairing takes place.
b. Unpaired electrons have parallel spin.
c. Half filled & completely filled orbitals give greater stability to atoms.

Exa: Chromium (Z = 24) and Copper (Z = 29) have anomalous electronic

configuration due to this reason.

Electronic configuration of Chromium is  Ar  4 s1 3d 5 but not  Ar  4s 2 3d 4

Electronic configuration of Copper is  Ar  4 s1 3d 10 but not  Ar  4s 2 3d 9

d. Pairing starts in p-subshell with 4th electron, in a d-subshell with 6th

electron and in an f-subshell with 8th electron.
e. According Hund’s rule Nitrogen atom has three unpaired electrons.
f. The completely filled or half-filled sub-shells have symmetrical
distribution of electrons in them and are therefore more stable.

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M. P. I. ATOMIC STRUCTURES XI

g. Electrons of same spin are present in sub-shell then they exchange their
positions release energy called exchange energy. The number of exchanges that
can take place is maximum when the sub-shell is either half-filled or
completely filled. Greater is the exchange energy, maximum will be the
stability.
h. Anomalous configuration is observed in the following cases:

Mo  42 : Kr  4d 5 5s1 , Tc*  43 :  Kr  4d 6 5s1

Ru  44 : Kr  4d 7 5s1 , Rh  45 :  Kr  4d 8 5s1

Pd  46 : Kr  4d 10 5s 0 , Ag  47 : Kr  4d 10 5s1

Gd *  64 : Xe  4 f 7 5d 1 6 s 2 , Tm*  69 :  Xe  4 f 13 6 s 2

Pt *  78 : Rn  4 f 17 5d 9 6 s1 , Au  79 : Rn  4 f 13 5d 10 6 s1

 * configurations are uncertain.

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M. P. I. ATOMIC STRUCTURES XI

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