II PU-PHYSICS 1

ATOMS
NOTE:
 In 1897, the experiments on electric discharge through gases carried out by the English physicist
J. J. Thomson revealed that interiors of different elements contain identical negatively charged
constituents.
 However, atoms, or the basic building blocks of matter are electrically neutral.
 Therefore, an atom must also contain some positive charge to neutralise the negative charge of the
electrons.
 But the arrangement of the positive charge and the electrons inside the atom was not known.

Thomson’s Atomic model (plum pudding model)

 The first model of atom was proposed by J. J. Thomson in 1898.
 According to this model, the positive charge of the atom is uniformly distributed throughout the
volume of the atom and the negatively charged electrons are embedded in it like seeds in a
watermelon.
 This model was also called plum pudding model of the atom.
 However subsequent studies on atoms showed that, the distribution of the electrons and positive
charges are very different from that proposed in this model.
Need for a new model of the atom:
 It was observed that, Condensed matter (solids and liquids) and dense gases at all temperatures
emit electromagnetic radiation in the form a continuous spectra with different intensities.
 This radiation is considered to be due to oscillations of atoms and molecules, governed by the
interaction of each atom or molecule with its neighbours.
 In contrast, light emitted from low density gases (such as neon or mercury vapour) has only
certain discrete wavelengths (line spectra).
 In such gases, the average spacing between atoms is large. Hence, the radiation emitted can be
considered due to individual atoms.
 In the early nineteenth century it was also established that each element is associated with a
characteristic spectrum of radiation.
 For example, hydrogen always gives a set of lines with fixed relative spacing between the lines. This
fact suggested an intimate relationship between the internal structure of an atom and the
spectrum of radiation emitted by it.
 In 1885, J J Balmer obtained a simple empirical formula which gave the wavelengths of a group of
lines emitted by atomic hydrogen.
The new atomic model was needed to explain all the above experimental observations.

GEIGER-MARSDEN EXPERIMENT FOR

THE SCATTERING OF PARTICLES

 Ernst Rutherford in 1906, he

proposed a classic experiment of scattering of
-particles by atoms to investigate the atomic
structure.
 This experiment was later performed
around 1911 by Hans Geiger and Ernst
Marsden.
 Explanation of the results of their
experiment led to the birth of Rutherford’s
planetary model of atom.
II PU-PHYSICS 2

 A beam of -particles emitted from a Bismuth radioactive source at a thin metal foil made of gold of
thin thickness 2.1 × 10–7 m
 The scattered alpha-particles were observed through a rotatable detector consisting of zinc
sulphide screen and a microscope.
 The scattered alpha-particles on striking the screen produced brief light flashes or scintillations.
 These flashes may be viewed through a microscope and the distribution of the number of scattered
particles may be studied as a function of angle of scattering.

EXPERIMENTAL CONCLUSIONS ARRIVED BY RUTHERFORD IN THE - SCATTERING EXPT.

 The entire mass of the atom is concentrated in the nucleus of an atom.
 The entire charge is concentrated in the nucleus rather than distributing throughout the volume
of the atom.
 The size of the nucleus is estimated to be of the order of 10-15 m and the size of an atom is about
10-10 m.
 The size of the electron is negligibly small and space between the electron and nucleus is almost
void.
 Electrons move circularly around a nucleus in different orbits depending on their energy.
 Atom as a whole is electrically neutral.
 Electron is acted upon by a force and hence it is not in the state of static equilibrium.
 To explain the Hydrogen spectrum, Rutherford proposed the idea of radiating circular orbits.
 For the stability, he assumed that the centripetal force is balanced by electrostatic force of
attraction.
i.e,

TOTAL ENERGY OF ELECTRON IN A HYDROGEN ATOM (in terms of its orbit radius.)

The Rutherford nuclear model of the atom pictures the atom as an electrically neutral sphere consisting
of a very small, massive and positively charged nucleus at the centre surrounded by the revolving
electrons in their respective dynamically stable orbits.
The electrostatic force of attraction, Fe between the revolving electrons and the nucleus provides the
requisite centripetal force (Fc) to keep them in their orbits.
Thus, for a dynamically stable orbit in a hydrogen atom

Thus the relation between the orbit radius and the electron velocity is
………….
And
………………(2)
If is the Kinetic energy of revolving electron, and € • be the potential energy of the system of
nucleus and electron, the total energy of the electron orbit is given by
‚€
„
‚ †‡ˆ‰Š 1 ‹Œ• 2 Ž
(The negative sign in U signifies that the electrostatic force is in the –r direction.)
„
‚
•
II PU-PHYSICS 3

„
•

The total energy of the electron is negative. This implies the fact that the electron is bound to the nucleus.
If E were positive, an electron will not follow a closed orbit around the nucleus.

INSUFFICIENCY OF RUTHERFORD’S MODEL

 If a charged particle moves in a circle, then it is being constantly accelerated.
 According to classical electromagnetic theory, an accelerating charged particle emits radiation in
the form of electromagnetic waves.
 As a result, the energy of an accelerating electron should decrease continuously.
 Then, the electron would spiral inward and eventually fall into the nucleus.
 Thus, such an atom cannot be stable.
 Further, according to the classical electromagnetic theory, the frequency of the electromagnetic
waves emitted by the revolving electrons is equal to the frequency of revolution.
 As the electrons spiral inwards, their angular velocities and hence their frequencies would change
ch
continuously, and they would
ould emit a continuous spectrum.
 This is in contradiction to the line spectrum actually observed.
 Thus, the Rutherford’s model was insufficient to explain the atomic structure completely.

ATOMIC SPECTRA:
 A spectrum is the ordered arrangement of wavelengths obtained from a source.
 When a low density gas under lower pressure is excited, it gives charesteristic lines against a dark
background (emission spectra)..
 When the light from a source is passed through an element at low
lower
er temperature, then, certain
wavelengths appear to be missing against the bright background of the original spectra
(Absorption spectra)
 These lines corresponding to a definite emitted or absorbed wavelength are the characteristic of the
substance which produces it. Thus, we can say that a line spectra Emission/absorption) is “the
finger print of an atom”.

SPECTRAL SERIES
 Hydrogen is the simplest atom and
therefore, has the simplest spectrum.
 In the observed spectrum, the spacing
between spectral lines within certain sets of
the hydrogen spectrum decreases in a
regular way (see Fig).
 Each of these sets is called a spectral
series.

BALMER FORMULA
 In 1885, the first spectral series
was observed by a J J Balmer in the visible region of
the hydrogen spectrum.
 This series is called Balmer series .
 The spectrum consists of a line with the longest
wavelength in the red region, called
alled as H =656nm.
 The next line in the bluegreen,
bluegreen called H =486
nm.
 Thehe third line in the violet is called H =434nm
and so on.
II PU-PHYSICS 4

 As the wavelength decreases, the lines appear closer together and are weaker in intensity.

Balmer found a simple empirical formula for the observed wavelengths

‘’ „ “
•
Where 8 is the wavelength, R is called Rydberg constant, and n =3,4,5,……
NOTE:
 The quantity, (1/8) is known as the wavenumber of a spectral line, measured in m-1
 The value of Rydberg constant is found to be R =1.097 × 107 m-1.
 If we put n=3 in the Balmer formula, we get the wavelength corresponding to H " line (656 nm).
 If we put n=4 in the Balmer formula, we get the wavelength corresponding to H $ line (486 nm).
 If we put n=5 in the Balmer formula, we get the wavelength corresponding to H ( line (434 nm). And
so on.

SPECTRAL SERIES OF HYDROGEN ATOM

Hydrogen atom has a single electron. Its spectrum consists of series of spectral lines. Which can be
obtained using a formula,

‘ „
•
Where R is Rydberg constant, n1 and n2 are positive integers.
Lyman series : Lyman Series consists of spectral lines corresponding to the transition of an electron
from higher energy orbits n1 = 1 and n2 = 2,3,4…

‘ „
•
These lines belong to Ultraviolet region.
Balmer series: Balmer series consists of spectral lines emitted during transitions of electrons from
higher energy orbits to the second orbit. n1 = 2 and n2 = 3,4,5… .

‘ „
•
These lines lie is the visible region.
Paschen series :Paschen series consists of spectral lines emitted when electron jumps higher energy
orbits to the third orbit n1 = 3 and n2 = 4,5,6 … .

‘ „
• ”
These lines lie in the infrared region.
Brackett series : Brackett series consists of spectral lines emitted during transitions of electrons from
higher energy orbits to fourth orbit. n1 = 4 and n2 = 5,6,7…

‘ „
•
These lines lie in infrared region .
Pfund series : Pfund series consists spectral lines emitted during transition of electrons from higher
energy orbits to the fifth orbit. . n1 = 5 and n2 = 6,7,8… .

‘ „
• •
These lines lie in infrared region .

NOTE:
 The transition from (n1 + 1) to n1, corresponding to Ist member or longest wavelength of the
series.
II PU-PHYSICS 5

 The transition from (infinity) state to ‘n1’ state corresponds to the last number or Series limit or
shortest wavelength of the series.

BOHR MODEL OF HYDROGEN ATOM:

 In 1912, Niels Bohr made certain modifications in the Rutherford’s atomic
model.
 Bohr combined classical and early quantum concepts and gave his theory of
atomic structure in the form of three postulates.

POSTULATES OF BOHR’S THEORY OF HYDROGEN ATOM:

1) An electron cannot revolve round the nucleus ONLY in certain permitted orbits called
STATIONARY ORBITS. Electron does not radiate energy in a stationary orbit.

2) Bohr’s Quantum Condition:

The radius of the allowed electron orbits is determined by the quantum condition.
It states that, THE ORBITAL ANGULAR MOMENTUM of electron about the nucleus can take only
—
integral values of the multiples of – ˜
—
i.e, – ˜
Where n =1,2,3,……..and h = Planck’s constant

3) Bohr’s Frequency Condition:

The atom emits radiation only when an electron Jumps from higher energy stationary orbit E 2 to a
lower energy orbit E1 such that the frequency of emitted photon, < can be calculated as
„
™
—
Where, h = Planck’s constant

NOTE:
 Plank's constant has the same unit as that of angular momentum (Js - joule second).
 Stationary orbits are also known as non-radiating orbits.
 Bohr's model also assumes that
(i) the nucleus is of infinite mass and is at rest
(ii) mass of the electron remains a constant.
 The gravitational force between the nucleus and the electron is weaker than electrostatic force by a
factor of 10–40 and its contribution to the centripetal force can be neglected.
 A circular orbit is considered as a stationary orbit if its circumference contains integral number of
de Broglie wavelengths.
 HYDROGENIC ATOMS:
These are Hydrogen-like atoms are ions in which only one electron will be revolving round the
nucleus of charge 'Ze', in a stationary orbit. Eg. He+, Li++
II PU-PHYSICS 6

EXPRESSION FOR RADIUS OF A STATIONARY ORBIT:

Consider an atom of atomic number Z. Let an electron of mass 'm' and charge ’–e' revolve round the
nucleus in a stationary orbit of radius 'r' with a linear velocity 'v'.
The centripetal force required for circular motion is provided by the electrostatic force of attraction
between the nucleus and the electron.

š
where Ze is the charge on the nucleus.
Î

Ze2
= ....... (1)
4pÎ0

—
According to Bohr's Quantisation condition,
n h
or .........(2)

› m v r n h 4 Î0
Consider • = 2
œ mv 4 Ze2

OR radius of nth orbit,

—
š
Where rn ® radius of nth orbit of electron, 0 ® permitivity of free space ; h ® Planck's constant.

For Hydrogen atom, Z=1

—

NOTE:
 From the above equation, it is clear that µ for given Z.
 Hence r1 : r2 : r3 : .... = 1 : 4 : 9 : ..... Therefore orbits of electron of an atom are not equally
spaced.
 The radius of innermost orbit (n=1) of Hydrogen atom (Z=1) is known as Bohr radius.
 It is denoted as r0 or a0. . •”ƒÅ
 The radius of nth orbit of an atom of atomic number Z is also given as,
š
1
 For given n, µ Z
, i.e the radius of a particular orbit decreases as the atomic number of atom
increases.

EXPRESSION FOR ORBITAL VELOCITY OF ELECTRON:

Consider an atom of atomic number Z. Let an electron of mass 'm' and charge '–e'
revolve round the nucleus in a stationary orbit of radius 'r' with linear velocity 'v'.
The centripetal force required for circular motion is provided by the electrostatic
force of attraction between the nucleus and the electron.

mv 1 Ze Ze2
OR ...... (1)
r 4p r 4p 0
II PU-PHYSICS 7

—
From Bohr's Quantisation condition, ...... (2)

1 mv Ze2 2p
Consider
2
• mvr
=
4pe 0 nh

(OR) Velocity of the electron in the nth orbit,

Ze2
.
2 nh

For Hydrogen atom, Z=1,

\ Velocity of electron in the nth orbit of Hydrogen,
e2
2 nh
NOTE:
 From above equation, it is clear that µ š/ . For given Z, OR
 µ / i.e., the orbital speed of electron in outer orbits falls by the factor ' '. In other words,
electron will have higher velocity in inner orbits.
e2 6 –1
 For the first orbit of Hydrogen atom, n=1, Z=1 = 2.18×10 ms
2 h
Z
 Expression for velocity of electron of Hydrogen like atom can be written as n
 Period of revolution of electron in nth orbit is given by
ž For the first orbit of Hydrogen atom, period of revolution, T = 1.53x10–16s.
1 ”.ƒ
 As µ and µ n
, ž µ

EXPRESSION FOR TOTAL ENERGY OF ELECTRON:

Consider an atom of atomic number Z. Let an electron of mass 'm' and charge '–e' revolve round the
nucleus in a stationary orbit of radius 'r', with a linear velocity 'v'.
The electron possesses potential energy due to the presence of electric field of the nucleus and kinetic
energy due to its motion.
Potential energy of electron,
= Potential at a distance r from nucleus × Charge on electron
1 Ze 1 Z
=„ ×e =„ ........ (1)
4p r 4p r
Kinetic energy of electron, Ÿ ½
mv 1 Ze 1 Ze
But e
• mv2 = e
r 4p r 4p r

1 1 Ze
Hence Ek = ....... (2)
2 4 Î r

Total energy of electron in the nth orbit is En = Ep + Ek

1 Z 2 1 1 Ze 1 Z 2
En „ ‚ –ƒ„ ‚ ƒ ˜
4 Î r 2 4 Î r 4 Î r
II PU-PHYSICS 8

1 1 Ze
(OR) En „ ........... (3)
2 4 Î r

n2 h2
But r = Ew ƒhav ¡ p m Z e2

1 Ze2 m Z e2
Hence En „ ¢
2 4 Î0 n 2 h2

š
„
• —

For Hydrogen atom, Z = 1

„
• —
NOTE:
 The negative sign indicates that the electron is in a bound state and energy must be
supplied, to remove it from an atom. The negative sign also indicates that the zero of
potential energy of the electron is at an infinite distance from the nucleus.
Z2
 From eqn (4), it is clear that µ n2. For a given atom, µ / . Thus as the value of n
increases, energy of electron also increases (it becomes less negative). In other words, an
electron in an outer orbit will have more energy than that in an inner orbit.
 Energy of electron in the ground state (n=1) of Hydrogen atom,
me4 –19
£ = –21.775 x 10 J = –13.6eV
8e2o h

 Total energy of electron in nth orbit of Hydrogen like atom can be expressed as
13.6 Z2
£ •.
n2
 Ground state' is the normal state of an atom wherein electron will be revolving in the orbit of
smallest radius (i.e., the Bohr radius, a0), with lowest energy.
 Principal quantum number, ' ' is an integer which determines the values of radius of an orbit,
velocity and energy of electron in that orbit.
 From equation for energy, it is also clear that electron can have only certain definite values of
energy.
This is known as 'Energy Quantisation'
Ep
 It can be shown that En – Ek = .
2

EXPRESSION FOR WAVE NUMBER OF SPECTRAL LINES OF HYDROGEN ATOM:

Consider the transition of an electron from a higher orbit n2 of energy E2 to a lower orbit n1 of energy E1
in hydrogen atom. Let E be the energy of the radiation (or photon) emitted. Then, according to Bohr's
postulate,

E = E 2 – E1
me4 me4
But, E1 = – and E2 = –
8Î2 2
o n1 h 8Î2 2
o n2 h

m 4 m 4
\ £ 8Î2o n2 2ƒ h
‚ 8Î2o n1 2ƒ h
II PU-PHYSICS 9

me4 1 1
E = ( — )
8 Î2
oh n2
1 n2
2
hƒC
But l
where is the wavelength of radiation.
hC me4 1 1
= ( — )
8 Î2
o h n2
1 n2
2
1 me4 1 1
= 3 ( — )
8Î2
o Ch n2
1 n2
2
1
But ¤ , wave number of the spectral line.
™
me4 1 1
¤=
\™ 3 ( — )
8Î2
o Ch n2
1 n2
2

¤
™ ‘ ¥ „ ¦

Where ‘ ƒ Rydberg constant.

• —”

This is the expression for wave number of spectral line emitted by a hydrogen atom.

EXPRESSION FOR RYDBERG CONSTANT:

Rydberg constant for any atom can be given by,

‘ ƒ
• —”
NOTE:
 Rydberg constant and the first obital enegy of hydrogen atom are related as
”.§
„ and ‘ ƒ which gives, ‘ ƒ „ •
• — • —” — —
 Wave number gives the number of waves present in unit length of the medium and is equal to
reciprocal of wavelength.
7 –1
 The value of Rydberg constant, R=1.097x10 m .
 Both Rydberg constant and wave number are expressed in m–1. Dimensional formula is [L-1].
 The wave number of spectral lines by hydrogen like atoms is
1 1
¤ = Z2 R (
™ –— ) where Z is the atomic number
n2
1 n2
2

ENERGY LEVEL DIAGRAM:

 It is a pictorial representation
of discrete energy states of
hydrogen atom in which
energy states are shown by
horizontal lines.
 These lines are separated by
vertical gaps of proper value.
Transition of electron between
any two states is shown by a
vertical arrow joining the two
states.
 The energy level diagram of
Hydrogen atom with its
II PU-PHYSICS 10

different spectral series is shown in the diagram.

NOTE:
 The energy of photon emitted due to transition between two states is proportional to the length of
the arrow joining the two states.
 As n value increases, the energy of electron increases (i.e., becomes less negative) but the energy
difference between the states decreases. The energy of electron becomes maximum (i.e., zero) for
n=¥ state.
 For larger values of 'n', the energy levels (or states) are too close that they form an 'energy
continuum'.
IONISATION:
The process of removing an electron from its orbit to an infinite distance from the nucleus is known as
'Ionisation' (Or, it is the process of removing an electron completely from the influence of nucleus)
Ionisation Energy
The energy required to remove an electron from its orbit to an infinite distance from the nucleus is known
as Ionisation Energy. It is expressed in eV.
 One of the methods to cause ionisation is to make the atom collide with an external accelerating
electron. An electron can be accelerated to high value by making it pass through a large potential
difference.
Ionisation Potential:
The minimum potential difference required by an electron to acquire kinetic energy just sufficient to
cause ionisation in an atom on collision is known as Ionisation potential. It is expressed in volts.
 Ionisation energy expressed in eV is numerically equal to ionisation potential expressed in V.
EXCITATION :
The process of shifting an electron from its orbit to any higher orbit by providing sufficient energy is
known as 'Excitation'.
Excitation Energy
The energy required to shift an electron from its orbit to any higher orbit is known as 'Excitation Energy'.
It is expressed in eV.
 One of the methods to cause excitation is to make the atom collide with an external accelerating
electron.
Excitation Potential
The minimum potential difference required by an external electron to acquire kinetic energy just sufficient
to cause excitation in an atom on collision is known as 'Excitation potential'. It is expressed in volts.
 Excitation energy expressed in eV is numerically equal to excitation potential expressed in volts.
NOTE:
 Ionisation potential of hydrogen atom in its ground state is 13.6V.
\ Ionisation energy is 13.6 eV.
II PU-PHYSICS 11

 The ionisation energy of an electron in nth orbit of an atom = E¥ –En where E¥ =0.

 It can be shown that ionisation energy of Hydrogen atom in its ground state=(Rhc) eV and
ionisation potential=(Rhc/e) volt.
 Energy required to excite an electron from n1 state to n2 state

(i.e. excitation energy) = En2 – En1.

 For Hydrogen atom, first excitation energy (i.e., n1=1 and n2= 2 ) = E2 – E1 = –3.4+13.6 = 10.2 eV.
Thus the first excitation potential is 10.2 volt.
NOTE:
 When the spectral lines of Balmer series of Hydrogen atom (which lie in the visible region of
Electromagnetic spectrum), were observed using a powerful microscope, each spectral line was
found to consist of many closely spaced lines. This is known as fine structure of spectral lines.
MERITS OF BOHR'S THOERY :
i) It successfully explained the line spectrum of Hydrogen atom.
ii) The value of Rydberg constant calculated using Bohr's theory is in good agreement with the
experimental value.
iii) The value of ionisation energy of Hydrogen atom in ground state calculated using Bohr's
theory is in good agreement with the experimental value.
 Zeeman Effect:
When a source of radiation, giving a line spectrum is placed in a magnetic field of suitable
strength, each spectral line was found to split into several components. This phenomenon is
known as 'Zeeman effect'.
 Stark Effect
When a source of radiation, giving a line spectrum is placed in an electric field of suitable strength,
each spectral line was found to split into several components. This phenomenon is known as 'Stark
effect'.
LIMITATIONS OF BOHR’S MODEL:
1. It is applicable only to Hydrogen and Hydrogen-like atoms.
2. It could not explain the fine structure of spectral lines.
3. It could not give information about relative intensities of spectral lines.
4. It could not explain Zeeman and Stark effects.
5. It did not consider the relativistic variation of mass of electron.
II PU-PHYSICS 12

DE BROGLIE’S EXPLANATION OF BOHR’S QUANTISATION CONDITION (2 ND POSTULATE)

Louis de Broglie argued that the electron in its circular orbit, as proposed by
Bohr, must be seen as a particle wave.

In analogy to waves travelling on a string, particle waves too can lead to

standing waves under resonant conditions.
 It means that in a string, standing waves are formed when the total
distance travelled by a wave across the string is the integral multiple of a
fundamental wavelength.
 Likewise, for an electron moving in nth circular orbit of radius rn, the
total distance travelled by the electron in the orbit is the integral multiple of a
fundamental wavelength
i.e,
•

OR, • …………….
 From De -Broglie theory, we have,
—
• …………….
 where p is the momentum of the particle.
from (1) and (2), we have
—

OR,
—

 Which gives Bohr’s Quantum condition.

 Thus de Broglie hypothesis provided an explanation for Bohr’s second postulate for the
quantisation of angular momentum of the orbiting electron.
 This explaination reveals that, the quantised electron orbits and energy states are due to the
wave nature of the electron and only resonant standing waves can persist.