1.

0 ATOMIC STRUCTURE

1.1 Introduction in 1909 by oil drop experiment.

With the help of above data the mass of electron can
On the basis of various experimental science at the
be calculated and it is very much close to 9.1 × 10– 31
turn of 19th century Dalton proposed the chemical
kg.
description of atom under his theory of the atom
(year 1803). 1.2.1 Discovery of electron (Cathode rays)
1.1.1 Assumptions of atomic theory of John
Dalton
(i) All matter is madeup of atoms that are indivis-
ible and indestructible.
(ii) All atoms of an element are identical.
(iii) Atoms of different elements have different mass
and different properties.
(iv) Atoms of different elements combine in simple
whole numbers to form various compounds.
(v) Atoms cannot be created or destroyed, when the At relatively higher potential difference between the
molecule of a compound decomposes, its electrodes of discharge tube the following observa-
constituting atoms are recovered unchanged. tions are noticed on lowering the pressure inside
The demerits of Dalton’s thought is that he did not discharge tube.
When the pressure is reduced to 1/100 atm a
think about the different isotopes of various elements. coloured glow is observed between the electrodes of
1.2 Fundamental particles of atoms (e, discharge tube which shows that electrical conduc-
tion is occuring or say current is flowing between the
p and n) electrodes of discharge tube. When the pressure is
The electron was discovered by J.J. Thomson. He further reduced to 1/10000 atm (almost vacuum) the
determined e/m value of the electron by performing glow between the electrodes disappears but the
and studying the deflections of cathode rays in current continues to flow which can be proved by
electric and magnetic field. various manner.
The charge on electron is 1.6 × 10–19 C (4.8 × 10–10
statcoulomb) is initially determined by R.A. Millikan
 If a perforated anode is used, a faint greenish glow is
observed on the glasswall of discharge tube present A
Cathode Anode
behind the anode. This shows that some invisible rays
are emitted from the cathode these rays were called S N B
as cathode rays. Cathode rays were a great mystery C
throughout the later half of the nineteenth century.
By the down of the twenteeth century the work on the The negatively charged material particles constituting
enigmatic rays proved that they are a stream of the cathode rays are termed as electrons.
electrons. Reaching this understanding required many
experiments. The findings of these experiments are By equalising the value of electical force and magnetic
as follows. force acting over the electron moving in the space
where electric field of strength E and magnetic field
1.2.2 Properties of cathode rays of strength B is present in the manner parallel to each
(i) Cathode rays travel in straight path so produces
e E
shadow when obstructed by objects. other. The Thomson found that m  2 , where r is
(ii) Cathode rays has momentum (i.e. these are Br
consist of material particles) so they can rotate the radius of curvature of path attained by the electron
pedal wheel. when it moves in mag. field only. In the same manner
(iii) They can easily penetrate the thin foil of metals by balancing gravitational force & electrical force over
which can be explained by presence of mechani- the electron Milkan determined the charge on electron.
cal energy. By the above data the electron is well defined as it is
(iv) Cathode rays carry negative charge so they that fundamental particle which carries one unit
cause charging of the particles present in the gas negative charge (1.6 ´ 10 –19 C or 4.8 ´ 10 –10
through which they pass as well as when the 1
cathode rays pass through electric and magnetic statcoulomb) and has a mass nearly equal to
1837
fields, the rays are deflected. times of the H atom.
(v) Cathode rays strike a metal foil, the latter
becomes hot. When the gaseous pressure in discharge tube is very
(vi) They produce x-ray when they strike to the atom low then the cathode rays emitted from the material
of hard metal like tungsten, molybdenum etc. of cathode metal and when the gaseous pressure in
(vii) They produce flourescence (emission of visible dischange tube is not much low then the cathode rays
spectrum) when strike to the glass wall as well (electrons) are produced by ionisation of gas particles.
as to certain other suitable substances like ZnS.
(viii) They affect the photographic plates.
buildup (1) :
For cathode rays the value of e/m -
Fluorescence where (a) Is independent of the nature of the cathode
gas cathode rays imping
or on the glass wall (b) It is independent of the nature of gas filled in the
air or ZnS screen
Cathode Anode (Metal Cross) dischage tube
(c) In SI system it is l.7588 × 1011
(d) All of the above are correct
Shadow of
Metal Cross) Ans. (d)
Sol.
Cathode rays consists of electrons and also called as
electron beam or e-beam.
1.2.2 Discovery of proton (Anode rays or
Cathode Anode
positive rays)
The Goldstein observed that along with cathode rays
some other rays were also coming in the direction
Pedal wheel
oposite to the cathode rays. These rays which were
coming towards cathode (away from anode) are ionised
particles of gas that was taken in the discharge tube
and known as anode rays like the cathode rays the anode

2
 rays also travel in straight path but the anode rays
Particle Mass No. Atomic No. Protons Neutrons Electrons
consist of positively charge particles.
Nitrogen atom – – – 7 7
The value of ratio charge/mass, as well as the individual Calcium ion – 20 – 20 –
value of charge and mass of the constituing particles Oxygen atom 16 8 – – –
of cathode rays do not change on changing the gas of Bromide ion – – – 45 36

dischange tube but in case of anode rays these values

Sol.
get changed on changing the gas taken in dischange
tube. Particle Mass No. Atomic No. Protons Neutrons Electrons

Experiments revealed that when hydrogen gas is taken Nitrogen atom 14 7 7 7 7

Calcium ion 40 20 20 20 18
inside the discharge tube then the particles present in
Oxygen atom 16 8 8 8 8
anode rays are H+. It is the discovery of proton. Bromide ion 80 35 35 45 36
A proton is defined as that fundamental particle which
carries on unit positive charge (1.6 ´ 10–19 C) and has Isotopes, Isobars, Isotones and isodiaphers :
a mass very nearly equal to that of H atom which is Isotopes : Atoms having same number of protons are
one unit mass on the atomic mass scale. known as isotopes. They always belong to same
Discovery of Neutron : element.
Moseley performed experiments to determine the Isotones : Atoms having same number of neutrons are
exact quantity of charge present on the nucleus. On k/a isotones. They belong to different element.
deviding this value by the charge of one proton we can Isobars : Atoms having same mass number are k/a
define the no. of protons present in that atom. isobars. They belong to different elements.
Therefore, the mass of the atom was calculated from
Isodiaphers : The difference in the number of neutrons
the number of protons present in that atom
and protons is same for isodiaphers. They belong to
(remembering that electrons have negligible mass).
different elements.
However for any element (except hydrogen) this mass
was found to be much less than the actual mass of that Isoelectronic : the two or more than two different
atom. This led to the idea that there must be some other chem. sp. (atoms/ions/molecules) containing the same
particles present in the atom and that these particles number of electrons are called isoelectronic with each
should be neutral but should have considerable mass. other.
Latter on Chadwick performed some scattering buildup (1) :
experiments by which certian new particles were
Arrange in the order of value of ratio n/p for
emitted which carries no charge but had a mass nearly
following particles (where n is the number of
equal to that of proton. This particle was termed
neutron and p is the numbr of proton)
neutron.
i) Protium ii) Deuterium
buildup (1) : iii) Tritium
Arrange in the orderof value of ratio charge/mass Thomson’s Model of Atom : J.J. Thomson, in 1904
for following particles Positive
Sphere
i) Alpha particle
ii) Beta particle
iii) Proton
Electron
Ans :
Proton > Alpha particle > Beta particle
Thomson's model of atom
2  4  0  (Water melon model)
1P 2 1
WAVE OPTICS

A is the expression used for showing composition Limitations of Thomson’s Model : It could not
ZE
of nucleus of an element in this expression A is mass satisfactorily explain the results of scattering
number (sum of number of neutrons and protons) experiments carried out by Rutherford.
and Z is atomic number (number of protons). -scattering experiments of Rutherford (1910):
5. Complete the following table by considering the
most stable isotope of given element :

3
 Rutherford in his experiment, directed high energy Nucleus
Electrons
s t r -particles from a radioactive source at
e a m s o f

the thin sheet of gold. In order to study the deflection

caused to the -particles, he placed a Zinc-sulphide
screen around the thin gold foil.
Spherical
ZnS screen

-rays

Block of lead

Rutherford's scattering experiments

From these experiments, he made the following

observations :–
(i) Most of the a-particles passed through the foil Nuclear Model of atom
without undergoing any deflection.
(ii) Few a-particles underwent deflection through Finding attributed to Rutherford’s model:
very small angles which is not more than 1°. The radius of atom of different elements is of the
(iii) Few -particles were deflected through angle as order of 10–10 m and radius of their nucleus is of the
large as 90°. order of 10–15 m.
(iv) Very few a-particles (only one in 20,000) were Nuclear radius r = r0A1/3
deflected back i.e., through an angle almost equal [A = mass number = number of proton + neutron
to 180°. r0 = proportionality constant = 1.2×10–15 m]
(v) Angle of deflection increases with increase in Failures of Rutherford’s model:
atomic number. On the development of concept of modern science,
From these observations, Rutherford drew the the Maxwell’s wave theory said that an accelerated
conclusion that the small heavy positively charge body charged particle (like electron) revolving in the field
present within the atom was called nucleus. of another charged particle like nucleus looses
Thus, according to Rutherford’s Model of atom the energy in the form of electromagnetic radiation and
atom consists of two parts; if this happen then orbit of the revolving electron
(i) Nucleus which is very small in size, carries should keep on decreasing and ultimatly electron
positive charge and in which the entrire mass of should fall into the nucleus and atom should collapse
the atom is concentrated. but this doesn’t happen actually. Hence the stability
(ii) Extra-nuclear part, i.e., space around the nucleus of Rutherford’s model get failed.
in which the electrons were distributed. It behaves
like empty space. Electromagnetic waves and its charac-
Rutherford’s Model of Atom : Nuclear model teristics:
(1911). Electromagnetic wave radiation:
The radiaitons consist of electric and magnetic
fields oscillating perpendicular to each other and
both perpendicular to the direciton of propogation
of radiation.

Direction of
wave propogation

Wavelength of a wave is defined as the distance

between any two consecutive crests or troughs. It is
represented by  (Lambda).

4
 
the radiations are called electromegnetic radiation of
Crest Crest
electromagnetic wave. The Maxwell stated that light
a rays are example of E.M. waves.
a Features of E.M. waves: Maxwell wave theory
Trough Trough (i) The electromagnetic radiation do not require any
medium.
Frequency of a wave is defined as the number of (ii) All electromagnetic radiation has velocity 3×108
waves passing through a point in one second. It is ms–1.
represented by  (nu) and its SI unit is Hertz (Hz) or (iii) The E.M. radiations show diffraction and
sec–1 or s–1. interference like other waves.
Velocity of a wave is defined as the linear distance (iv) According to wave theory the wave energy is
travelled by the wave in one second. It is determined by the wave amplitude as we know
reperesented by v or C. energy carried by wave depends on it’s amplitude.
In this manner Maxwell concluded the E.M. radiation
Amplitude of a wave is the height of the crest or the
are wave known as wave nature of E.M. radiation.
depth of the trough. It is represented by ‘a’ and is
By Maxwell’s thought we can not explain the findings
expressed in the units of length.
of black-body radiation as well as outcomes of
Wave number is defined as the number of waves photoelectric effect. Hence electromagnetic wave
present in unit length. Evedently, it will be equal to theory of Maxwell was successful in explaining those
the reciprocal of the wavelength. It is represented by properties of light which arise due to wave nature of
 (termed as nu bar). light.

1
Planck’s quantum theory:
 Planck stated that the radiation is not continuous while
it consist of discontinuous energy packets or bundles.
Relationship between velocity, wavelength and
Each bundle is known as quantum and it is also known
frequency of a wave:
as photon in case of light.
Since all the electromag. rad. travel with same velocity.
Energy of each quantum is directly proportional to the
Hence the various electromagnetic radiation should be
frequency of radiation.
differentiated either by the value of l or by the value
of n. E.
Hence, E = h.
 decreases
C G X U V I M R [Where h is planck’s constant (6.62×10–34 J sec)]
The amount of total enery absorbed or emitted by a
infinity to 3  1020 7.9  1014 to 3.95  1014 1  109 to 1  105
body will be whole number integral multiple of energy
As frequency is the number of waves passing through of quantum associated with that radiation.
a point per second and  is the length of each wave,
nhc
hence their product will give the velocity of wave. Total emitted or absorbed energy =

 = speed
6. Calculate the no. of photons emitted by 60 Watt
Heat radiations lie under the range of infrared. bulb in 10 hrs. When light of wavelength 6000 Å
Cosmic rays always consist of an extra particle which is emitted by it.
is either alpha or beta or positron.
Sol.
Maxwell electromagnetic wave theory: E  h  n
Maxwell described that light is a transverse
nhc  6.5  1024
electromagnetic wave and proposed the =

electromagnetic wave theory of light.
WAVE OPTICS

The high frequency vibrating charge particle has an Findings of Planck’s quantum theory
E.M. wave associated with it. The radiaitons consist (i) Black body radiation: It is observed that on
of electric and magnetic fields oscillating changing (increasing) temperature of black body or any
perpendicular to each other and both perpendicular other such body ther is not only intensity of radiation
to the direciton of propogation of radiation. but the change in color of radiation is also observed as
The radiation posses wave character and travel with the follows:
velocity of light because of the above characteristics

5
 0 is threshold frequency & h0 is known as work
function W0 of that particular metal substance.
 is the frequency of incident light, hence h is
energy of photon of incident light.
m is the mass of electron (9.1×10–31 kg) and v is
velocity of that emitted photo electron.
2. The Wien ‘s law states that the surface
temperature of a hot black body is inversely
proportional to the wavelength corresponding to
1
maximum intensity as T   and constant of
max

The above experimetal ressult cannot be expained proportionality = 2.9 mmK. The maximum
satisfactorily on the basis of the Maxwell wave theory intensity of solar radiation occurs at 490 nm.
of light. Planck suggested that atoms and molecules What is the temperature of the surface of sun?
could emit (or absorb) energy only in discrete Sol.
quantities.
On applying Wien’s law
(ii) Photoelelcltric effect: When certain metals
3
T  2.9  10 7mK
(having good photosensitivity like K, Rb, Cs etc) were
exposed to light electron were ejected. 4.9  10 m
= 5.9 × 103 K
8. The threshold frequency v0 for a metal is 6 × 1014
s–1. Calculate the kinetic energy of an electron
emitted when radiation of frequency v = 1.1 ×
1015 s–1 hits the metal.
Sol.
1 m V2
K.E. = = h(v – v0)
2 e
 K. E. = (6.626 × 10–34)(1.1 × 1015 – 6 × 1014)
Dual nature of electromagnetic radiation: By
The phenomenon is called photoelectric effect. The Einstein (1905)
findings observed in this experiment are as follows From the above observations we conclude that some
(i) The electron current is proportional to the intensity properties of light (or of other radiations) can be
or brightness of light. explained only if we consider light to have wave nature
(ii) For each metal, there is a characteristic minimum whereas some other properties of light or any other
frequency 0 (termed as threshold frequency) radiation such as black body radiation and protoelectric
below which the photoecletric effect is not effect can be explained if we consider light to have
observed. As well as when the incident frequency particle nature. Thus light is said to have a dual nature.
 > 0 , the ejected electrons came out with certain 7. Certain sun glasses having small of AgCl incor-
Kinetic Energy. The kinetic energy of these porated in the lenses, on expousure to light of
emitted photo-electrons increase with the appropriate wavelength turns to gray colour to
increase of frequency of light used. minimise the glare by following reaction:
The threshold frequency 0, incident frequency  AgCl   Ag  Cl
hv
& kinetic energy of emitted elctron can be related
If the heat of reaction for the photolysis of AgCl
by conservation of energy as follows
is 248 kJ mol–1, what maximum wavelength is
needed to induce the desired process?
h  h0  1 mv 2
2 Sol.
Energy needed for required photolytic change
= 248 × 103 J/mol

6
If photon is used for this purpose, then according to of energy. The greater the distance of the orbit
Einstein one molecule absorbs one photon. There- from the nucleus, more shall be the energy
fore, associated with it. These orbits are also called
energy levels and are numbered as 1, 2, 3, 4 .... or
 NA. hc  248  103
 K, L, M, N, .... from nucleus outwards.

6.626  1034  3.0  108  6.023  1023 (vii)When an electron jumps from one stationary orbit
= to another. There is emission or absorption of
248  103
= 4.83 × 10–7 m energy in the form of radiation is always observed;
DE = Ehigh – Elow = hn
Bohr’s model of atom & Bohr’s postulates:
(i) The atom has a nucleus where all the protons and Bohr applied different law of mechanics &
neutrons are present. It is present at the centre of defined various postulates as follows :
the atom.
(ii) Negatively charged electrons are revolving around (1) Radii of various orbits :
the nucleus in a same way as the planets are
revolving around the sun. The path of the electron
is circular.
Since the circular motion is a non-uniform motion,
hence always requires a force over the moving body.
a) The force acting in the line of velocity vector is
responsible for change in magnitude of velocity.
b) The force acting perpendicular to the line of
velocity vector is responsible for change in
direction of velocity.
In any given circular motion if the motion is periodic
then only b force is required which can be obtained by mv2
r
is the required value of force by which the electron
any natural (physical) force like gravitational attractive
force or electrostatic attractive force present in that is maintained at circular orbital of radius r. The required
situation. The required value of this force is equal to mv2
mv2/r. value of is obtained by electrostatic force
r
(iii) Since the body/particle moving in a circular path present between the revolving electron & nucleus.
always possess the momentum known as angular
momentum. The value of which depend on mass mv2 k Ze2
 2
of moving body, magnitude of velocity & the r r
radius of circular path and expressed as mvr.
q1q2
(iv) The angular momentum of electron is quantized Electrostatice force 
r2
i.e. electron can possessed only those value of
angular momentum which are an integral multiple q1q2
= k
of h/2p known as quantisation of angular r2
momentum of revolving electron. Out of
infinite number of possible circular orbits around k(Ze)e
=
the nucleus, the electron can revolve only in those r2
orbits whose angular momentum is an integral
For the given case the value of k in S.I. units is 9 ´ 109
multiple of h/2p. These specified orbits are called
and in CGS units is 1.
stationary orbits.
WAVE OPTICS

k Ze2
nh v2  — (1)
Angular momentum = rm
2
(v) Each stationary orbit and so the electron present Since a definite value of angular momentum possess
in that orbit is associated with a definite amount by the revolving body which is equal to mvr.

7
 According to quantisation of angular momentum of
Radius of 2nd orbit of H atom n22 z1
rd +2 = z  n2
hn Radius of 3 orbit of Li atom 2
electron mvr 
1
2
4
=
nh 3
v — (2)
2 mr (2) Velocity of revolving electron :
Putting the value of v in eqn. (1), k Ze2
We know v 2  r m — (i)
n 2h 2 kZe2
 nh
4 m r
2 2 2 mr Also we know v  2 r m — (ii)
n 2h 2
 kZe2
42mr Dividing (i) by (ii) we get,

n2 h2 v2 k Ze2 2 r m
r — (3)  .
42 m k Ze2 v rm nh
h2
The value of is a constant & can be calculated 2  k Ze2
42me2k v
nh
in CGS system as follows :
(6.626  1034  107 erg s)2 Z
4  (3.14)  9.1  1031  103 gm  4.8  1010statcoul.  1
2 v  2.18  106 . m /s
n
= 0.529  108 cm = 0.529Å
2 k e2
On keeping the value in eqn. (3),  2.18  106 m /s
h
0.529  108 n 2 0.529n 2 5. Determine the Bohr orbit of Li2+ ion in which
rn  cm  Å
Z Z electron is moving at speed equal to the speed of
(The rn is radius of nth orbit of an atom or ion having electron in the first Bohr orbit of H-atom.
no. of p = Z) Sol.
For the nth orbit of H, For H like species
rn  0.529  108 n 2cm  0.529n 2Å Z
v = 2.18 × 106 × ms–1
n
For the ground state of H atom,
Now, let us consider that in Li2+ the electron is in nth
orbit.
radius of H atom = 0.529Å
Speed of electron in nth Bohr orbit of Li2+ is
9. Calculate ratio of radius of 2nd orbit of H atom to
3rd orbit of Li+2 ion : 3
v = 2.18 × 106 ×
n
Sol.
Now, applying the condition of equal speed:
n2
Since rn  2.18 × 106 ×
3
= 2.18 × 106
Z n
 n=3
n22 z1 4
Hence z  n2  3 6. Determine the number of revolutions made by
2 1
electron in one second in the 2nd Bohr orbit of
buildup (18) hydrogen atom.

Calculate ratio of radius of 2nd orbit of H atom to Sol.

3rd orbit of Li+2 ion. The number of revolutions made by electron in one
second would be

8
 rps  v  
2 r 13.6(2)2  12  1 2 
(1) (2)   15
rps  nh  

42mr 2
( v  nh ) 13.6(2)2  1 2  1 2 
2mr (3) (4) 
nh
2 Energy level diagram:
= 42m  a 0n 
2
 Z  (i) Orbit of lowest energy is placed at the bottom
  and all other orbits are placed above this.
(ii) The gap between two orbits is proportional to the
h.Z2 energy difference of the orbits.
= 42ma 2n3
0
= 8.23 × 1014 Revolutions per sec
(3) Energy of an electron :
Let the total mechanical energy of the electron be E.
It is sum of kinetic energy and potential energy.
E = K.E. + P.E.
P.E. = Electrostatic Potential Energy

kq1q2  k(Ze)e
= =
r r

1 k Ze2
E  mv2 
2 r
Putting the value of mv2 from equation (1),

kZe2 kZe2 kZe2

E  
2r r 2r
Putting the value of r from equation (3),
22 Z2k 2me4
E — (4)
n 2h 2
Energy level diagram of H-atom
1313Z2 kJ 22k 2me4 1313kJ
E 
NA n 2 h2 NA Various terms and their values for unielectronic
atom/ion
Ground state: It is lowest energy state. It is defined
when electron is situated in first orbit. For various
1313Z2
E kJ/mole unielectronic atom or ion the ground state energy =
n2 – 13.6 Z2 eV
Excited state: States of atom or ion where it has
Energy per electron per atom E can be expressed in
energy higher than ground state are called excited state.
different units as follows:
When electron is present in 2nd orbit then it is said to
1313kJ  Z2 
 13.6eV  2   Rydberg  2  be first excited state of that atom or ion. Hence n th
Z2 Z2
E  
NA  n 2
n  n  excited state means electron is present in ‘n + 1’ orbit.
WAVE OPTICS

16. The ratio of (E2 – E1) to (E4 – E3) for He+ ion is Excitation energy: Energy required to move an
approximately equal to (where En is the energy of electron from ground state to any higher state of the
nth orbit) atom is called excitation energy.
(a) 10 (b) 15
(c) 17 (d) 12
Ans. (b)

9
 First excitation energy of an unielectron atom or ion
9 E for He
= Energy of 2nd orbit – Energy of 1st orbit. or E1 for Li+2 =
4 1
= [– 3.4 Z2 – (– 13.6 Z2)]eV
= 10.2 Z2 eV 9
= 19.6  1018 
4
Excitation potential: It is the potential difference –18
= 44.10 × 10 J/atom
through which an electron must be eccelerated so that
Thus the energy of the first stationary state of Li+2
it move from ground state to any higher state. 1st
will be – 44.1×10–18 Joule/atom.
excitation potential of an unielectron atom or ion =
10.2 Z2 volt buildup (1) :
2nd excitation potential of an unielectron atom or ion If the binding energy of 2 nd excited state of
= 2nd excitation energy deivided by e = 12.09 Z2 volt hydrogen like sample is 24 eV approximately, then
Ionisation energy (I.E.): The limiting amount of the ionisation energy of the sample is
energy required to move an electron from ground state approximately.
to the state of n   is called ionisation energy.. Sol.
I.E. of an unielect. atom or ion = 13.6 Z2 eV per atom. 13.6(Z)2
 24
Ionisation potential (I.P.): The I.E. devided by e (3)2
becomes I.P. of that unielectron atom or ion. I. E. = 13.6(Z)2
= (24 × 9)
Binding energy: The amount of energy required to
= 216 eV
move an electron from any state to n   is called
binding energy or seperation energy of that state. Spectroscope and spectrum: An instrument which is
The binding energy for nth state of an unielectron atom used in study to define the composition of the
or ion = Energy of infinite orbit – energy of nth orbit radiation. Early spectroscopes were simply prisms
with graduations marking all wavelenths of light or say
= 0 – Energy of nth orbit
of visible spectrum. The modern spectroscope are
13.6 Z2 eV complex instruments and they cover the wide range of
= per atom radiations. The pattern of the emergent radiation
n2
recorded on the film is called as spectrogram.
10. A single electron system has ionization energy
11180 kJ mo1–1. Find the number of protons in
the nucleus of the system. White Light
Source
Ans.
Z=3
Diffraction
Sol. grating

13.6Z2 ev
I. E. =
n2

Z2  21.69  1019 J / atom

= ( ev = 1.6×10–19 J)
n2

11180  103  Z2  21.69  1019


6.023  1023 12
m
tru
ec

12. The ionization energy of He+ is 19.6 × 10–18 J

Sp

atom–1. The energy of the first stationary state of

Li+2 will be-
Sol.
E1 for Li+2 = E1 for H × Z2Li = E1 for H × 9
E1 for He+ = E1 for H × Z2He = E1 for H × 4

10
 Spectrum Spectrum
Based on nature Based on origin

Continuous Discrete Absorption spectrum Emission spectrum

Absorption spectrum: When a continuous electro-

Band spectrum Line spectrum magnetic radiation consist of various frequencies is
first passed through the chemical substance and then
Continuous spectrum: analysed by spectroscope, it is observed that certain
frequencies are missing in the obtained spectrogram.
It is known as absorption spectra.
Emmission spectrum: The radiation emitted due to
an atom or molecule making a transition of e from a
high energy state to a lower energy state.
When hydrogen gas at low pressure is taken in the
discharge tube and the radiation emitted on passing
electric discharge is examined with spectroscope. The
obtained spectrogram is called emmission spectrum
of hydrogen.

[Ordinary white light is dispersed by prism into Hydrogen spectrum: Its historic background.
continuous spectrum.] On the behalf of spectroscopic data of hydrogen
All the frequencies continuing from 3800 to 7600 Å spectrum the Balmer (a mathematician) noticed that a
are present in the given band, so it is an example of particular wavelength had a relation to every line in
continuous spectrum. the hydrogen spectrum that was in the visible light
region. By which Balmer (year 1885) gave the equation
Band spectrum: to calculate all possible wavelength of emmission that
occur in the range of visible spectrum.

    2
n2 
 , where B is constant and equal to
 n  m2 
364.50682 nm, m is equal to 2 and n is an integer
such that n > m.
Frequency
In year 1888 the Physicist Johannes Rydberg gave a
Various continuous frequencies in the form of empirical formula to calculate wavelength which is
different bands are seperated by absent frequencies 1 1 1
applicable to all series  R H  2  2  , where RH
making band spectrum. e.g.: Finding of molecular   n1 n2 
spectrum.
4
Line spectrum: is and known as Rydberg’s constant.
B
Hydrogen spectrum by Bohr’s model
When electron in an excited atom comes back from
higher orbit (n2) to lower orbit (n1) then it emits a
photon, having energy equal to difference in energy
WAVE OPTICS

levels.
Frequency

The series of spectral lines seperated by absent n2 h

frequencies making line spectrum. .e.g.: Atomic
spectrum like spectrum of H atom.
n1

11
 h  E  En2  En1 Since the same photons first break the covalent bond
and then excite the two H-atoms to their 3rd Bohr’s
Rydberg Z2  Rydberg Z2  orbits simultaneously. Hence, transition energy
h   
n22  n12  provided by this photon is twice that of an atom of H.
Energy consumed in transition = 2E
 
h  Rydberg Z2  12  12  = 2 × 1.938 ×10–18 J
 1
n n 2
= 3.876 × 10–18 J
1  R Z2  1  1  Energy needed to break a covalent bond
 H  n2 n2  = (4.598 – 3.876) × 10–18 J
1 2
= 7.22 × 10–19 J
Rydberg
R H is k/a Rydberg constant = Bond energy per mol
hC
Hence Bohr’s model provides theoretical = 7.22 × 10–19 J × 6.023 × 1023
explanation of H spectrum. = 434.86 kJ
11. What are the frequency and wavelength of a Different series in Hydrogen spectrum
photon emitted during a transition from n = 5
state to the n = 2 state in the hydrogen atom? PASCHEN
E R BR
LM
Sol. BA AC
KE
TT
Since nhigher = 5 and nlower = 2, this transition gives rise
to a spectral line in the visible region of the Balmer

PF
UN
series.
AN

D
LYM

HUMPH
18 J 
1  1
E = 2.18  10
22 52 

R EY
= 4.58 × 10–19 J energy emmited. 0 – 3.4 – 13.6 1 2 3 4 5 6 7
The frequency of the emmited photon is given by
LYMAN SERIES nf = 1, ni = 2, 3, 4, 5, .....
E  4.58  1019 J
v= Ultraviolet
h 6.626  1034 Js
BALMER SERIES nf = 2, ni = 3, 4, 5, 6, .....
= 6.91 × 1014 Hz Visible
8. A sample of Hydrogen gas (H 2) in a flask is PASCHEN SERIES nf = 3, ni = 4, 5, 6, 7, .....
irradiated by light of wavelength 432.25 Å so that Infrared
all hydrogen, after atomisation, gets excited to 3rd BRACKETT SERIES nf = 4, ni = 5, 6, 7, .....
Bohr orbit. Assuming no energy loss occurs to the Infrared
surroundings; determine the bond energy of H2 in PFUND SERIES nf = 5, ni = 6, 7, .....
kJ/mol unit. Infrared
Sol. HUMPHREY SERIES nf = 6, ni = 7, 8, .....
Infrared
Since the part of energy of photon is utilized in
breaking of the covalent bond and remaining energy Spectra lines of Hydrogen atom:
goes in the process of transition of electron.  Lyman Series is the first spectral series of H
The energy associated with incident photon = h atom and it was found in 1898 by Lyman.
14
It’s value of n1 = 1 and n2 = 2, 3, 4, .....
 6.625  10  310 10
8

432.25  10 1  R 1  1 
H 2
1 n2 
 2 , where n2 is always > 1
–18
= 4.598 ×10 J
Now the transition energy per H-atom,  Balmer Series is the second series of H-

 
spectrum and it was found in 1892 by Balmer.
1
E = 2.18 × 10–18 1  9 J It’s value of n1 = 2 and n2 = 3, 4, 5, .....
1 R 1  1
= 1.938 × 10–18 J H 2
2 n2 
 2 , where n2 is always > 2

12
  Paschen Series is the third series of H- the following diagram
spectrum and it was found by Paschen.
It’s value of n1 = 3 and n2 = 4, 5, 6, ..... e
E2
1 R 1  1  E3 e
H 2
3 n2 
 2 , where n2 is always > 3
E1= E2 + E3
E1 1= 2 + 3
 Brackett Series is the fourth series of H- e
spectrum and it was found by Brackett.
It’s value of n1 = 4 and n2 = 5, 6, 7, .....
1 R 1  1
H 2
4 n2 
 2 , where n2 is always > 4
Now, let us assume that initially electron was in nth orbit.
 Pfund Series is the fifth series of H-spectrum In 1st type of transition, it descends to 2nd orbit.

n1  14
and it was found by Pfund.
It’s value of n1 = 5 and n2 = 6, 7, 8, .....  – 27eV = kZ2 2 — (i)
1 R 1  1  In 2nd type of transition, electron descends from n to
H 2
5 n2 
 2 , where n2 is always > 5
the 3rd orbit.

n1  19
Humphrey Series is the sixth series of H-
spectrum and it was found by Humphrey.  – 10.125 eV = kZ2 2 — (ii)
It’s value of n1 = 6 and n2 = 7, 8, 9, .....
From equation (i) and (ii)
1 R 1  1
 H 2
6 n2 
2 , where n2 is always > 6

1  1  2.67 1  1
n2 4 n2 9 
Lines get closer and closer together
and eventually reach the 'series limit'.  n=6
Now, using equation (i)
1 1
– 27 eV = 13.6VZ2 36  4  
 Z=3
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 15. Calculate wavelength for 2nd line of Balmer
Frequency (PHz) series of He+ ion
Paschen series Balmer series Lyman series
(infra-red) (partly visilble) (ultra-violet) Sol.

10. A unielectronic atom (atomic number Z) is in 1  R(2)2  1  1 

 n 2 n 2 
higher excited state of energy level ‘n”. This excited  1 2
atom can make a transition to the first excited state n1 = 2 n2 = 4
by successively emitting two photons of energy 10
1  R(22 )  1  1 
eV and 17 eV respectively. Alternatively, the atom
 22 42 
from the same excited state can make a transition
to 2nd excited state by emmiting photons of energy 1  3R   4
4.175 eV and 5.95 eV, respectively. Determine Z and  4 3R
n. [where R is Rydberg constant]
Sol. 20. Which transition of the Hydrogen spectrum
WAVE OPTICS

If the electron moves from the higher orbit to the would have the same length as the Balmer
lowest one in a number of successive steps, the sum of transition, n = 4 to n = 2 of He+ spectrum -
energies of all photons is always equal to the energy of (a) n2 = 2 to n1 = 1 (b) n2 = 3 to n1 = 1
photon emitted had the electron jumped the highest (c) n2 = 4 to n1 = 2 (d) n2 = 5 to n1 = 3
orbit to the lowest one in a single step as described in
Ans. (a)
For He+ ion Z = 2,  can be expressed as

13
 wavelengths. Among these ten different
1  R Z2  1  1   R [2]2  1  1  wavelengths, seven wavelengths are smaller than
 H n 2 n 2  H
 22 42 
 1 2 the incident wavelength  andonly two of them
3R have wavelengths longer than the incident
= —(i) wavelength. Determine the orbit number in which
4 H
Now for H atom electrons were present initially.
Sol.
1 R 1  1 The total number of emitted spectral lines are seven
H 2 2 —(ii)
  n1 n 2  hence, the higher orbit number nhigher can be
Equating equs(i) and (ii) we have calculated as follows.
n(n  1)
1  1 3 10  (n = nhigher)
n12 n 22 2 2
 nhigher = 5
Obviously n1 = 1 and n2 = 2. Hence the transition n =
2 to n = 1 in hydrogen atom will have the same length It shows that after absorbing light of wavelength ,
as the transition n = 4 to n = 2 in He+ species. the electron reached to fifth orbit. Since it is
provided that initially atoms were in the excited state,
Various terms related to spectrum therefore possibility of nlower being in the 1st orbit is
 First line of any spectral series is the longest ruled out. Now the left possibility for them being are
wavelength line (or say line of least frequency in 2nd, 3rd or 4th orbits.
as well as line fo least wave number). This line If nlower = 4
is associated with the photon of least energy. It means the electron of original sample of H is
present in 4th orbit. But is not the correct answer.
1  R Z2  1  1  In this case, no emission line will have energy greater
max H  n2 (n  1)2 
1 1 than the energy of incident photons.
 Last line of any spectral series is the shortest Hence nlower = 4 does not satisfy the given situation.
wavelength line (or say line of highest If n = 3
frequency as well as line of highest wave It means the electron of original sample of H is
number). This line is associated with the photon present in 3rd orbit. The deexcitation of electron
of highest energy. from 5th orbit to ground state is evolving total ten
different wavelengths. Among these ten
1  R Z2  1  1  R H Z2
 n2 2  = n2 5  1, 4  1, 3  1,5  2, 4  2, 3  2,2  1 are
min H
1 1
those seven (mentioned in question) & 5  4,4  3
This last line is also known as series limit. The
wavelength associated with this is known as are other two (mentioned in question) and the 10th is
wavelength of marginal line and calculated as transition of electron 5  3 which emit radiation of
follows. same wavelength as that of incident light.
wavelength of marginal line of any series 11. An excited hydrogen atom was allowed to relax to
n12 ground state and the emitted light was thrown on
= R Z2 . another glass tube containing excited He + ions
H
where the electrons in He+ ion were excited to
 Maximum number of different photons that can further higher orbit. At the end, all the excited He+
be emmitted when an electron jumps from any was allowed to relax to the ground state and the
higher state n2 to another state n1 is equal to most energetic photon was found to possess energy
n(n  1) equal to 52.88 eV. Determine the orbit number in
where n is n2 ~ n1. which electrons were present initially in H-atom
2
and He+ ion.
17. A glass tube containing sample of H-atoms in some
Sol.
excited state. They are irradiated with light of
wavelength  and atoms get re-excited to further Since most energy loosing transition of He+ is from
higher orbit. On removing the light source, atoms nth orbit to 1st orbit expressed as follows

 
de-excite to ground state with emission of
1
radiations. The emission spectrum thus obtained 52.88 = 13.6 × (2)2 1  2
n
which consists of ten spectral lines of different

14
 n comes equal to 6 1  3R
Let initially the electrons were present in (n1) orbit in  4
H-atom and n2 orbit in He+ ion initially. As H-atom de-
excites from n1 to first orbit, He+ ion gets excited from  4
n2 to sixth orbit. 3R
Hence, according to the conservation of energy 19. If electron make transition from 7th excited state
to 2nd energy level in H atom sample find the
   
k 1  12   k  42  42  max. number of spectral lines observed.
 n1 H  2
n 6 He Sol.
 n2 = 2, n1 = 3
n(n  1)
22. The shortest wave length in H spectrum of Lyman Number of spectral lines =
2
series when RH = 109678 cm–1 is-
Sol.  
6 1 7
= 6 2  6  2 = 21
For Lyman series n1 = 1
21. Estimate the difference in energy between 1st and
For shortest ‘’ of Lyman sereis the energy
2nd Bohr orbit for a H atom. At what minimum
differnece in two levels showing transition should be
atomic number, a transition from n = 2 to n = 1
maximum (i.e. n2 = ).
energy level would result in the emission of X-
1  R  1  1   109678 ray with  = 3.0 × 10–8 m. Which hydrogen like
H 2
 1 2  species does this atomic number corresponds to -
  = 911.7 × 10–8 = 911.7 Å Sol.
25. Let n1 be the frequency of series limit of lyman E1 for H = – 13.6 eV
series, n2 be the frequency of 1st line of lyman
series, n3 be the frequency of series limit of  E2 for H = (–13.6/22) = –13.6/4 = –3.4 eV
Balmer series. Then find relation between n1, n2  E2 – E1 = –3.4 – (–13.6) = +10.2 eV
and n3
For trasition from 2nd to 1st energy level with
Sol. emmision of  = 3.0 × 10–8 m
 1  R . Z2  1  1 
E1 E3  12 22 
H

E2 1  1.09  107  Z2  3
3  108 4
E1 = E2 + E3  Z=2
 h1 = h2 + h3 15. Determine the first three transitions in He+ ion
 n1 = n2 + n3 emitting lights in the visible range of
buildup (1) : electromagnetic radiation as well as the ones
common in the emission spectrum of hydrogen
Calculate the wavelength of 2nd line of Balmer atom.
series of He+ ion. Sol.
1  R(2)2  1  1  The H-atom (Z = 1) shows Balmer lines in visible
Sol.   n2 n2  range for which
1 2

n1 = 2, n2 = 4 1  R 1  1 
H where n = 3, 4, 5, ....
1  R(2)2  1  1   4 n2 
WAVE OPTICS

 22 44  For He+ ion (Z = 2) the wavelengths of emission

15
 250 to 468.7 nm.
1  R Z2  1  1  4 4
 H  n2 n2  = R H  2  2  14. What electronic transition in He+ would emit light
1 2  n1 n2  of same wavelength as that of 1st Lyman line in H-
For the lines of similar wavelengths. atom?
Sol.
1  1    4  4 
 4 n2   n12 n22  Lyman line corresponds to transition from 2nd to 1st
orbit.
Now the 1st Balmer line in H-atom occurs at n = 3 Hence wavelength corresponding to the given
and solutions of n1 and n2 are as follows transition of H can be determined as
11 4  4 1  R 1  1 
 H ( Z = 1) — (i)
4 9 n12 n22  1 4
 n1 = 4, n2 = 6 For He+ ion, wavelength of a photon emitted when an
2nd Balmer line in H-atom occurs at n = 4 and electron undergoes transition from higher orbit n1 to
solutions of n1 and n2 are as follows lower orbit n2 can be expressed as

1 1  4  4 1  R Z2  1  1 
  n2 n2 
4 16 n12 n22  H
2 1

 n1 = 4, n2 = 8
1R 4  4
3rd Balmer line in H-atom occurs at n = 5 and H 2
 n2 n1 
or  2 — (ii)
solutions of n1 and n2 are as follows
Since, according to the conditions given in question,
1 1  4  4
 4 25 n12 n22
both wavelengths determined by expressions (i) &
(ii) are identical,
 n1 = 4, n2 = 10
Hence, the desired transitions are: 1  1   4  4 
1 4  n22 n12 
6  4, 8  4 and 10  4.
11. Determine series limits of wavelengths in the
Paschen series of He+ ion. 1  42  n2 = 2
n2
Sol.
1 4
1  R Z2 1  1  and 4  n2  n1 = 4
where, n = 4, 5, 6, .... .
9 n2 
1
 H
The following points support Bohr’s theory :
Fot shortest ,
(i) The freq. of the spectral lines calculated from
1  4R Bohr’s eqn. are in the agreement with the freq.
min 9 H ( n = ) observed experimentally in hydrogen spectrum.
(ii) The spectra of hydrogen like species such as
min  9 He+, Li+2, Be3+ can be explained with the help
4R H of Bohr’s theory.
= 205 nm Limitations of Bohr’s theory :
For maximum , (i) It does not explain the spectra of multi-electron
1  4R 1  1  7R H atoms.
H
max 9 16 = 36 (ii) When a high resolving power spectroscope is
used, it is observed that a spectral line in the
1  36 hydrogen spectrum is a collection of several
 max 7R H lines which are very close to one another. Bohr’s
theory does not explain the fine spectra of even
= 468.7 × 10–9 m
hydrogen atom.
= 468.7 nm
(iii) It does not explain the splitting of spectral lines
Hence, the required series limit in the term of  is

16
 into a group of lines under the influence of 10–31 kg and h = 6.6 ´ 10–34 kg m2 s–1)
magnetic field (Zeeman effect) and electric
Ans : 7.25 ´ 10–7 m
field (Stark effect).
(iv) It is not in agreement with Heizenberg’s Bohr’s theory in relation to De Broglie
uncertainity principle. Equation :
Wave nature of electrons (De Broglie’s One of the postulates of Bohr’s theory is that angular
momentum of an electron is an integral multiple of
hypothesis) :
h/2. This postulate can be derived with the help of De
De Broglie extended the idea of wave particle duality Broglie equation.
and he suggested that all the moving body (matter) has
Consider an electron moving in a circular orbit around
features of both as material particle and as a wave
nucleus. The wave would be associated with the circular
known as matter wave.
orbit. If the two ends of the electron wave meet to give
De Broglie derived an expression for relating the regular series of crests and troughs, the electron wave
wavelength and momentum of the motion of body. is said to be in phase, i.e., the circumference of Bohr’s
 = mc2
h orbit is equal to whole number multiple of the
wavelength of the electron wave.
hc  mc2
or So, 2pr = nl

2 r
 h  h h or  — (i)
or n
mc mv P
De broglie equation is applicable in all the case of
moving particle/body but has no significance for large
particles because the wavelength decreases if the value
of mass(m) increases and so the wave nature of their
motion becomes insignificant.
30. An electron beam can undergo diffraction by
crystals. Through what potential should a beam
of electrons be accelerated so that its wavelength
From de-Broglie’s eqn.,
becomes equal to 1.54 Å.
h
Sol.  — (ii)
mv
We know that
h 2 r
1 mv 2  eV Thus, 
, V is that potential. mv n
2
h
h or v  h or v 2  h2 or mvr  n. [v = vel. of electron and
and  = 2
mv m m22
r = radii of the orbit]
1m h2 eV
 Angular momentum = n.
h
2 m 2 2 i.e.
2
— (iii)

1 m  h2 2 This proves that de-Broglie and Bohr-concepts are in

or V=  1  h2 perfect agreement with each other.
2 m   e 2 m  e
2 2

Substituting the values, we get Heisenberg Uncertainity Principle :

Since the trajectory of any moving body/particle can
1 (6.62  1034 )2
V = 2  9.108  1031  (1.54  1010 )2  1.602  1019
only be defined when the position & velocity. (or
WAVE OPTICS

momentum) of that particle are known

= 63.3 volt simultaneously.
Werner Heisenberg presented a principle known as
buildup (3) : Heisenberg uncertainty principle which states :
A moving electron has 4.55 ´ 10–25 J of kinetic “It is impossible to measure simultaneously the
energy. Calculate its wavelength (mass = 9.1 ´ exact position and exact momentum of a moving

17
 body.” Thus, uncertainty principle is very significant in the
The uncertainty of measurement of position, Dx, and case of smaller moving particles like electrons and
the uncertainty of momentum, Dp or Dmv, are related other subatomic particles.
by Heisenberg’s relationship as
E
x. p  h / 4 where, h is Planck’s constant. As we know x = vt and P 
v
The minimum value of product of Dx DP can never be xP = Et
h (where E is the uncertainity in kinetic energy).
less than and so.
4

h h
x P  =
4 2

h
x  v 
4 m

31. A golf ball has a mass of 40 g, and a speed of 45 m/

s. If the speed can be measured within accuracy of
2%, calculate the uncertainty in the position.
Sol.
The uncertainty in the speed is 2%,

i.e., 45  2  0.9 m s–1.

100

h
Using the equation x =
4mv

6.626  1034
= 4  3.14  40  103 (0.9ms1)

= 1.46 × 10–33 m
This is nearly ~ 10–18 of the diameter of a typical
atomic nucleus. It shows that the uncertainity in
position is very extremely low.
Hence, the uncertainity principle is not meaningful
for such large body.

buildup (3) :
Calculate the uncertainty in position assuming
uncertainty in momentum within 0.1% for :
(a) a tennis ball weighing 0.2 kg and moving with
a velocity of 10 m/s.
(b) a electron moving in an atom with a velocity
of 2 ´ 106 m/s.
Ans : (a) 2.635 ´ 10–32 m
(b) 2.89 ´ 10–8 m
For an electron (mass = 9.10 ´ 10–28 g), the product
of uncertainty is quite large.
In the case of bigger particle (having a considerable
mass), the value of the product of uncertainty is non-
considerable.

18
Quantum mechanics function of the electron,  is the reduced Plank’ss
Introduction constant having value h/2, me is the mass of the
electron, and E is the total energy of the electron.
Quantum mechanics or quantum physics is the branch
In addition to being time-independent, U(r) is also
of modern science which deals with quantum particles
spherically symmetrical.
like photon, electron etc.
This suggests that we may solve space dependent
Now instead of physical description these particles are wave function by Schrodinger’s equation more easily
described mathematically by wave function. if we express it in terms of the spherical coordinates
Please, do not be confused with wave nature of (r,,) instead of rectangular coordinates (x,y,z). A
spherical coordinate system is shown in figure. In
electron. The wave particle duality is a seperate spherical coordinates, the variable r is the radial
discussion. coordinate,  is the polar angle (relative to the
The quantum mechanics deals through theoretical vertical z-axis), and  is the azimuthal angle (relative
science known as wave mechanics which is based on to the x-axis). The relationship between spherical
wave function. The wave function is the tool which and rectangular coordinates is
mathematically describes the electron. The total wave x = rsin  cos , y = rsin sin , z = rcos.
function is the function of position in space & time
and expressed as (x, y, z, t). It can be seperated into space
dependent and time dependent parts, those are
expressed seperately (x, y, z) and (t).

Schrodinger Model of the atom

The hydrogen atom is the simplest atom in nature so
it is a good starting point to study atomic structure.
The hydrogen atom consists of a single negatively
charged electron that moves about a positively
charged proton. For the special case of a hydrogen
atom, the force between the electron and proton is
an attractive Coulombic force.
The proton is approximately 1800 times more Figure: The relationship between the spherical and
massive than the electron, so the proton moves very rectangular coordinate systems.
little in response to the electrostatic force of The factor rsin¸ is the magnitude of a vector formed
interaction by the projection of the polar vector onto the xy-
With the assumption of a fixed proton, we focus on plane. Also, the coordinates of x and y are obtained
the motion of the electron. In the electric field of by projecting this vector onto the x- and y-axes,
the proton, the potential energy of the electron is respectively. The inverse transformation gives
2 r  x 2  y2  z 2 ,
U(r)  k e , where k  1 and r is the distance
40

r
between the electron and the proton.   cos1 z ,
r
Notice that the potential energy function U(r) does
not vary in time. As a result, we are most interested   cos1  x 
 x 2  y2  .
in the space dependent part of the Schrodinger’s  
equation of the hydrogen atom. Since the U(r) is spherically symmetrical that is
2  d2 d2 d2 
why this equation reduces to three simpler
 ћ  2  2  2   U(r)  E equations: one for each of the three coordinates (r,,
2me  dx dy dz  and ). Therefore solutions to the time independent
WAVE OPTICS

(i) For discussion in class people like to express wave function are written as a product of three
the time independent Schrodinger’s equation for functions:
one dimenstional space (one dimentional box).
2  d 2 
 ћ  2   U(x)  E
2me  dx 
where  = (x,y,z) is the three-dimensional wave

19
  (r,  ,  ) =R(r)  ( )  ( ) Quantum
numbers Quantum state of that electron
n, l, m of & it's wave function
is the radial function is the polar function is the phi
dependent on the dependent on the function of electron
radial coordinate r polar coordinate   only n = 1, r
only only 1 e  a0
100  1 3/2
l = 0,
ml = 0  a0
Quantum Number and Quantum States:
n = 2, r
The valid solutions to Schrodinger’s equation
 200  1 1  2  r  e 2a0
(r,,) are labeled by the quantum numbers n, l, and 4 2 a0  a0 
l = 0, 3/2
m. ml = 0
The possible solutions of differential equation for R n = 2, r
1 r e 2a sin e–i
depends only on n & l; similarily polar function  l = 1,  21–1  1 3/2 0

8  0 a0
a
depends only on l & m and  depends only on m. ml = –1
The dependence of each function on quantum n = 2, r
numbers is indicated with subscripts as follows: l = 1,  210  1 3/2 1 r e 2a cos 0

nlm(r,,) = Rnl(r) lm() m() ml = 0 4 2 a 0 a 0

Hence these three quantum numbers are findings of r
Schrodinger’s equation. n = 2, 1 r e 2a sin ei
 211  1 3/2 0
l = 1, 8  a0 a0
n : principal quantum number,
ml = 1
l : angular momentum quantum number
m : angular momentum projection quantum number Table: Wave functions for electron of the Hydro-
Any perticular set of quantum number (n, l, m) is gen Atom
known as quantum state. (i) Certain wave functions are free from angular
Not all sets of quantum numbers (n, l, m) are part as they are having l = 0.
possible. For example, the orbital angular quantum (ii) Some of these expressions contain the letter i,
number l can never be greater or equal to the which represents 1 . When probabilities are
principal quantum number n(l < n). Specifically, we calculated, these complex numbers do not
have appear in the final answer.
n = 1, 2, 3, …,
For a given n, l = 0, 1, 2,…, (n – 1) By solving Schrodinger’s equation we determine the
For a given l, m = – l, (–l + 1),…, 0,…,(+ l – 1), + l wave function  of that quantum particle. But  directly
has no any physical significance.
buildup (3) : Probability Distribution:
For the hydrogen atom, how many possible Since the  has an imaginary root i (known as iota and
quantum states correspond to the principal
it is equal to 1 ). So it is complex function. If the
quantum number n = 1 as well as n = 2.
sign of i is reveresed then it will become complex
Sol. conjugate of that wave function. Let the  = Aei(kx – wt)
For the ground state, n = 1, l = 0, and m = 0. In other then it’s complex conjugate * will be equal to Ae–i(kx
words, there is only one quantum state with the wave – wt)
.
function for n = 1, and it is 100. However, for n = 2,
we have l = 0, and l = 1, For l = 0, m = 0, and for l = As we know that,  has no any physical significance,
1, m = –1, 0, 1. so the  multiplied by its complex conjugate.
Therefore, the allowed states for the n = 2 state are If the wave function is  & it’s complex conjugate is
200, 21–1, 210, and 211. *. The product of these two as * is also expressed
as ||2 and spoken as mode psi square.
For example, wave functions for the hydrogen atom
at various possible quantum states are given in table Let the Z = a + ib then it’s complex conjugate
as follows. Z* = a + – ib = a – ib
The Z*Z = (x + y)(x – y)
= x2 – y2

20
 = a2 – (ib)2 i  1, so (ib)2  b2  Probability density at dist. a0 2 (a0 )
  
Probability density at dist. 0 2 (0)
= a2 + b2. It will be real.
Hence, the mode psi square is real quantity and refers The radial wave function for 1s orbital of H
as probability distribution. Therefore we can use
3/2  r
quantum mechanics to make predictions about   1  1  e a0
physical events by the use of probability   a0 
statements. It is therefore proper to state, “An 2 (a0 ) (1 / a 03 )e2r/a0
electron is located within this volume with this  
2 (0) (1 / a30 )e0
probability at this time,” but not, “An electron
= e– 2
is located at the position (x, y, z) at this time.” = 0.14
buildup (3) : Hence in case of 1s orbital the probability of finding
the electron in a small region at a distance a0 from
Let us consider the wave function (obtained by nucleus is only 14% of that of finding the electron in
solving the S.E.) of a quantum particle is plotted a region of the same volume located at nucleus.
in a graph paper, it is as follows:
Normalisation of wave function: Non-useable
 form of wave functions are make useable by
normalisation.

buildup (3) :
Becomes Becomes zero at +  The probability distribution (*) of an electron
zero at –  0 x
present in one dimensional box having that
dimension equal to a is provided as follows:
Then what will be it’s probability distribution and


it’s significance.



a x
0
If the particle is not able to move through any
x
tunnel of the box then tell whether the given graph
0 is right or wrong.
Certain locations has zero probability while other It is wrong because the total probability of findings that
locations have non-zero value of probability of finding particle between x equal to 0 to a should not be more or
that particle. For these locations we can only compare less than 1.
the probability but we can not predict the exact location a
of that quantum particle. Hence, the value of 0 |  |2 dx must be equal to 1.It is
Now, two discussions arise one is normalisation of wave
known as normalisation condition.
function and other is collapse of wave function.
As we know the ||2 is * and  is determined by
18. Suppose the electron is in a 1s orbital of a hydrogen solving S.E.
atom. What is the probability of finding the a
electron in a small region at a distance ao from If 0 |  |2 dx is not coming 1 then we must multiply
the nucleus relative to the probability of finding certain constant (known as normalisation constant) to
it in the same small region located right at the the value of (Let A = 1)
WAVE OPTICS

nucleus? The radial wave function for 1s orbital

a
1 1  3/2 r So that 0 (1 * 1)dx must come 1. It is known as
of H is    a  e a0 , where a0 is Bohr’ss
 0 normalisation of wave function and 1 is known as
radius and r is radial variable. normalised wave function. In such case the solution of
Sol. S.E. is said to be  instead of .

21
 buildup (3) : Let we open that box and it will observed
(measured) that electron is present at a definite
The wave function for the box of dimension  is location. Let us confirm it as x7 then what will be
provided as  = eiknx means x is 0  x  . Define the probability distribution of this electron?
whether it is normaliesd or not.



 = e–iknx

0 |  |2 dx
x
 x7
 
0
= 0 eiknx.eiknxdx  eiknx.eiknx  e0
We did measurement by which the position of that

= 0 1dx quantum particle is determined, so the probability
distribution graph is collapsed. It is known as collapse
of wave function.
= x0
Orbital
= Orbital is the space in which the probability of finding
The given wave function eiknx is not normalised and the an electron is significantly good. Since we do not
normalised value of wave function  Aeiknx. specify the exact position and momentum of the
electron. Hence we do not define a definite path for
1 iknx the electron, rather we define only the probability of
= e
 the electron being in various space points around the
Normalisation constant A is calculated and equal to nucleus.
1/  . Orbital wave function
Once a wave function is normalised then it will remain According to the quantum mechanical model atomic
normalised for future. orbitals are described by wave functions. It is
To determine the probability of finding an electron composed of two parts, the radial part (r) & the angular
in a hydrogen atom in a particular region of space, it part (,) . The complete wave function of an orbital
is necessary to integrate the probability density is known as orbital wave function and expressed as
|nlm|2 over that region: follows:
Probability =  volume | nlm | 2dv   (r).(,)
where dv is an infinitesimal volume element. If this
integral is computed for all space, the result is 1,
because the probability of the particle to be located Radial part Angular part
 It depends on the  It is function of the
somewhere is 100% (the normalization condition).
distance (r) from the angle  and  w.r.t.
Collapse of wave function: Since the wave nucleus. different axes.
function is linear combination or say superposition of  It describes size of  It describes shape of
various wave functions. The wave function collapse orbital orbitals.
 It is related with  It is related with
occur when a wave function reduces to a single eigen
quantum number n quantum number l
state due to interaction with external world. This and l. and m.
interaction is called observation or measurement.
As we know that study of the variation of  with all
buildup (3) : these three variables is not possible in a single diagram
Let us consider an electron is present in a one simultaneously. It is why the radial part variation and
dimensional box having that dimension a. Then the angular part variation are studied in separate
plot the probability distribution graph of that diagrams.
electron between the limits as follows The wave functions of s-orbital is independent of
angular part.

Radial wave function of orbital: nl
It is the mathematical description of the electron of
that orbital. It is the function of distance (r) from the
a x
0

22
nucleus. The radial wave function for 1s and 2s orbital to zero (dP/dr = 0) and solve for r. The most
is as follows probable radial position is not equal to the average
or expectation value of the radial position because
|n00|2 is not symmetrical about its peak value.
nl nl

+
+ – r
r
(a) for 1s orbital (b) for 2s orbital
As we know that wave function has no physical
significance so please do not be confused with the
sign.
Radial probability density (2)
Probability density is a function used for various
statistical expressions. Here it is taken as the
probability of finding the electron in unit volume and
Figure: The radial probability density function for
it is expressed as 2 . The plot of probability density
the ground state of hydrogen.
and r for 1s and 2s orbitals is as follows: The radial probability is the total probability of finding
an electron in a radial shell between sphere of radii r
and (r + dr).
Since the volume of this spherical shell is equal to
  4r2dr, Hence radial probability is expressed as
Radial prob. = prob. density × vol. of radial shell
= 2 × 4r2dr
The radial probability distribution curves give the
r Node r
probability of finding the electron at a distance r from
(a) for 1s orbital (b) for 2s orbital the nucleus irrespective of direction.
Radial probability (4r2 2dr)
Let us consider an electron in a state of zero angular r = a0 = 0.529Å r = 5a 0= 2.7Å
4r22dr

4r22dr
momentum (l = 0). In this case, the electron’s wave
r = 0.8a0
function depends only on the radial coordinate r.
(Refer to the states 100 and 200 in Table ) The
infinitesimal volume element corresponds to a r r
Node

spherical shell of radius r and infinitesimal thick- (a) for 1s orbital (b) for 2s orbital
ness dr, written as dv = 4r2dr.
The probability of finding the electron in the region
r to r + dr (“at approximately r”) is
P(r)dr = |n00|24r2dr.
Here P(r) is called the radial probability density
function (a probability per unit length). For an
electron in the ground state of hydrogen, the
probability of finding an electron in the region r to
r + dr is
|n00|24r2dr = (4/a03)r2exp(–2r/a0)dr,
WAVE OPTICS

where a0 = 0.5 angstroms. The radial probability

density function P(r) is plotted in figure. The area
under the curve between any two radial positions, say
r1 and r2, gives the probability of finding the electron
in that radial range. To find the most probable radial
position, we set the first derivative of this function

23
 Angular probability density:  2
1s orbital 2s orbital 2p orbital l ml

It can be obtained by squaring the angular wave

function. The graph of angular probability density is
R R R drawn against different value of angles for given value
of l & m. This graph represents angular distribution of
electron density which is interpretated as shape of
orbital. For an s-orbit the shape remain spherical but
r r r for p & d-orbitals the plots however become more
elongated as compared to the graph of angular wave
function.
R
2
R
2
R
2 z z
y y
 
r node r r – + x x
4r R dr
4r R dr

4r R dr

2
2

(a) Angular part of the (b) Angular probability

2
2

wave function for function for

p -orbital
x p -orbital.
x

a0 r node r r
Angular nodes = l
Type of nodes and their numbers
Radial nodes = n – l – 1 Since r = r

Angular wave function of orbital:  l ml If (r 1)  0 , there exists a radial node. The radial node
The angular part of wave function is known as angular is a sphere with radi r1. Therefore the term spherical
wave function and expressed as , ), where  and  node (also know as circular node) and radial node are
are zenith and azimuthal angles, respectively. same.
The angular wave function is plotted as a polar graph  is further seperate as  If either  or
of angular function against different value of angles  is zero for a given respective angle value, there is
for given value of l and m. an angular node. Angular node could be a planar node
For s-orbital the angular wave function is independent or a conical node.  being zero corresponds to a
of an angle. Hence the graph is circular, which reflects planer node.  being zero corresponds to either a
the spherical shape of s-orbital. conical node or a planar node.
Overall there will be n – 1 nodes
Angular nodes = l
Radial/spherical nodes = n – l – 1
Shape of atomic orbitals
Shape of an atomic orbital is the diagram based on
angular probability density values constructed.
In case of p-orbital the plot of angular wave function For this purpose following two approaches followed
for pz-orbital involves angle  while those for px & py (i) Charge cloud diagram
orbital involve both  and . (ii) Boundary surface diagram

y y y Shape of s-orbital
z z z On the basis of quantum numbers, for s-orbital l and m
+ – + + values are zero. It means any s-orbital has one
x x x
orientation. The only shape having one orientation is
– – sphere. Hence, s-orbitals are non-directional as the
probability of finding the electron is equal in all
For 2px orbital For 2py orbital For 2pz orbital directions.

24
 z z z Nodes quantity.
1s 2s Node 3s
y y
Principal Quantum number (n) :
y
x The principal quantum number n is associated with
x x
the total energy of the electron, En. According to
Schrodinger’s equation:
Shape of p-orbital
Since for p-orbital (l = 1), there are three values of
magnetic quantum numbers (– 1, 0, + 1) are alloted.
 mek 2e4 
En =  
 2h2 
 n1  = E n1 
2 0 2

i.e. three possible orientations are possible. Hence,

p-orbitals are dumb-bell shaped with the electron where E0  13.6 eV.
distribution concentrated in identical lobes on either
side of the nucleus and seperated by a nodal plane that Notice that this expression is identical to that of
cuts through the nucleus. Bohr’s model. As in the Bohr model, the electron in
a particular state of energy does not radiate.
z z z
x x x For a hydrogen atom the total energy depends on
principal quantum number (n) only howerver for any
given principal quantum number there are more than
y y y one quantum state are possible and explained as
different angular momentum states.
py pz
px
Angular momentum quantum number (l) :
Nodal plane = yz Nodal plane = xz Nodal plane = xy
Cartoon representation of 2p orbitals The angular quantum number (l) is associated with
the orbital angular momentum of the electron in a
Shape of d-orbital hydrogen atom ( the only other part of angular
An orbital with l = 2 is called a d-orbital. There are momentum posses by electron is due to its spin and
five possible values of magnetic quantum number for discussed latter)
l = 2, i.e. – 2, – 1, 0, +1, +2. Thus d-orbital can have
any one of the five orientation. Four of the five d- angular momentum which arises due to orbital
orbitals are cloverleaf shaped and have four lobes of motion of electron is known as orbital angular
maximum electron probability seperated by two nodal momentum
planes through the nucleus. The fifth d-orbital is
similar in shape to a pz-orbital but has na additional Quantum theory tells us that when the hydrogen atom
donut shaped region of electron probability centred in is in the state nlm, the magnitude of its orbital
the x-y plane.
z z angular momentum is
L  ћ l (l  1)
where l = 0,1,2,…,(n – 1).
y x y x Quantum states with different values of orbital
angular momentum are distinguished using spectro-
dxy dyz scopic notation. The designations s, p, d, and f result
z z z from early historical attempts to classify atomic
spectral lines. (The letters stand for sharp, principal,
diffuse, and fundamental, respectively.), After f, the
letters continue alphabetically.
y x y x y x

dxz dx2 – y 2 dz 2
WAVE OPTICS

Physical Significance of the Quantum

Numbers
Each of the three quantum numbers of the hydrogen
atom (n, l, m) is associated with a different physical

25
 Orbital Angular State Spectros-copic
Quantum Momentum Name
Number l

0 0 s Sharp

1 2h p Principal

2 6h d Diffuse

3 12h f Fundamental

4 20h g

5 30h h

Figure: The relationship between Lz and L.

Table: Spectroscopic Notation and Orbital Angular
Momentum Substituting ћ l (l  1) for L and m for Lz into this
l=0 l=1 l=2 l=3 l=4 l=5 equation, we find mћ  ћ l (l  1) cos 
n=1 1s Thus, the angle  is also quantized with the particular
n=2 2s 2p values = cos–1(ml(l + 1)).
n=3 3s 3p 3d Both the polar angle () and the projection of the
n=4 4s 4s 4d 4f angular momentum vector onto an arbitrary z-axis
n=5 5s 5p 5d 5f 5g
(Lz) are quantized.
n=6 6s 6p 6d 6f 6g 6h
A detailed study of angular momentum reveals
Table: Spectroscopic Description of Quantum States that we cannot know all three components simulta-
neously. We already discussed that the z-compo-
Angular momentum projection quantum nent of orbital angular momentum has definite
number (ml) values that depend on the quantum number m.
This implies that we cannot know both x- and y-
The angular momentum projection quantum number
components of angular momentum, Lx and Ly, with
ml is associated with the azimuthal angle  and is
certainty. As a result, the precise direction of the
related to the z-component of orbital angular
orbital angular momentum vector is unknown.
momentum of an electron in a hydrogen atom. This
component is given by Lz  mћ , buildup (3) :
where m = – l, – l + 1, …, 0, …, + l – 1, l.
What Are the Allowed Directions?
Hence the z-component of angular momentum is
Calculate the angles that the angular momentum
quantised with it’s own quantum number m.
vector L can make with the z-axis for l = 1, as
So it has definite values that depend on the quantum
shown in figure.
number ml.
The z-component of angular momentum is related to
the magnitude of angular momentum by Lz = Lcos,
where  is the angle between the angular momentum
vector and the z-axis.
The direction of the z-axis is determined by
experiment-that is, along any direction, the
experimenter decides to measure the angular
momentum. For example, the z-direction might
correspond to the direction of an external magnetic
field (since experimenter apply certain external
factors while study).

26
 cos 3 = LzL = ћ2ћ = – 1 2 = – 0.707 ,
so that 3 = cos–1(–0.707) = 135.0°
Significance
The angles are consistent with the figure. Only the
angle relative to the z-axis is quantized. L can point
in any direction as long as it makes the proper angle
with the zaxis.
Thus, the angular momentum vectors lie on cones,
shown in figure. Which approaches 1 as l becomes
very large. If cos = 1, then = 0º. Furthermore, for
large l, there are many values of ml, so that all angles
become possible as l gets very large.
Can the magnitude of Lz ever be equal to L?

Using the Wave Function to Make Predictions

As we saw earlier,
In a more advanced course on modern physics, you
will find that |nlm|2 = nlm*nlm, where nlm*
is the complex conjugate. This eliminates the
occurrences of i = –1 in the above calculation.

If the electron has orbital angular momentum (l  0),

then the wave functions representing the electron
depend on the angles  and ; that is, nlm = nlm
(r, , ). Atomic orbitals for three states with n = 2
and l = 1 are shown in figure. An atomic orbital is a
region in space that encloses a certain percentage
(usually 90%) of the electron probability. (Some-
times atomic orbitals are referred to as “clouds” of
Figure: The component of a given angular momen- probability.) Notice that these distributions are
tum along the z-axis (defined by the direction of a pronounced in certain directions. This directionality
magnetic field) can have only certain values. These is important to chemists when they analyze how
are shown here for l = 1, for which m = –1,0, and atoms are bound together to form molecules.
+1. The direction of L is quantized in the sense
that it can have only certain angles relative to the z-
axis.
Strategy
The vectors L and Lz (in the z-direction) form a
right triangle, where L is the hypotenuse and Lz
is the adjacent side. The ratio of Lz to |L| is the
cosine of the angle of interest. The magnitudes L =
|L| and Lz are given by L  l(l  1)ћ and Lz = mћ .
Solution
We are given l = 1, so ml can be +1, 0, or – 1. Thus,
L has the value given by L  l(l  1)ћ  2ћ
The quantity Lz can have three values, given by
Lz  mlћ  {ћ,ml  10,ml  0  ћ,ml  1
WAVE OPTICS

As you can see in figure, cos = Lz/L, so for m =

+1, we have cos1 = LZL = ћ2ћ = 12 = 0.707.
Thus, 1 = cos–10.707 = 45.0°.
Similarly, for m = 0, we find cos2 = 0; this gives 2
= cos–10 = 90.0°.
Then for ml = –1:

27
 8.2 Orbital Magnetic Dipole Moment
of the Electron
Learning Objectives
By the end of this section, you will be able to:
• Explain why the hydrogen atom has magnetic
properties
• Explain why the energy levels of a hydrogen
atom associated with orbital angular momentum
are split by an external magnetic field
• Use quantum numbers to calculate the magni-
tude and direction of the orbital magnetic
Figure: The probability density distributions for dipole moment of a hydrogen atom
three states with n = 2 and l = 1. The distributions In Bohr’s model of the hydrogen atom, the electron
are directed along the (a) x-axis, (b) y-axis, and (c) moves in a circular orbit around the proton. The
z-axis. electron passes by a particular point on the loop in a
A slightly different representation of the wave
function is given in figure. In this case, light and dark certain time, so we can calculate a current I  Q . An
t
regions indicate locations of relatively high and low
electron that orbits a proton in a hydrogen atom is
probability, respectively.
therefore analogous to current flowing through a
In contrast to the Bohr model of the hydrogen atom,
circular wire . In the study of magnetism, we saw that
the electron does not move around the proton
a current-carrying wire produces magnetic fields. It
nucleus in a well-defined path. Indeed, the uncer-
is therefore reasonable to conclude that the
tainty principle makes it impossible to know how the
hydrogen atom produces a magnetic field and
electron gets from one place to another.
interacts with other magnetic fields.

Figure (a) Current flowing through a circular wire

is analogous to (b) an electron that orbits a proton
in a hydrogen atom.
The orbital magnetic dipole moment is a measure of
the strength of the magnetic field produced by the
orbital angular momentum of an electron. From
Force and Torque on a Current Loop, the magnitude
of the orbital magnetic dipole moment for a current
loop is µ = IA,
where I is the current and A is the area of the loop.
(For brevity, we refer to this as the magnetic
moment.) The current I associated with an electron
in orbit about a proton in a hydrogen atom is

Figure: Probability clouds for the electron in the I e — (8.14)

T
ground state and several excited states of hydrogen.
where e is the magnitude of the electron charge and
The probability of finding the electron is indicated
T is its orbital period. If we assume that the electron
by the shade of color; the lighter the coloring, the
travels in a perfectly circular orbit, the orbital period
greater the chance of finding the electron.
2 r
is T  — (8.15)
v
where r is the radius of the orbit and v is the speed

28
of the electron in its orbit. Given that the area of a magnetism called the Bohr magneton, which has
circle is r2, the absolute magnetic moment is the value 9.3×10–24 joule/tesla (J/T) or 5.8×10–5
eV/T. Quantization of the magnetic moment is the
  IA  e r 2
 
result of quantization of the orbital angular
2 r
v momentum.
As we will see in the next section, the total magnetic
evr dipole moment of the hydrogen atom is due to both
= — (8.16)
2 the orbital motion of the electron and its intrinsic
It is helpful to express the magnetic momentum µ in spin. For now, we ignore the effect of electron spin.
  
terms of the orbital angular momentum (L  r  p)
Because the electron orbits in a circle, the position buildup (3) :
 
vector r and the momentum vector p form a right What is the magnitude of the orbital dipole
angle. Thus, the magnitude of the orbital angular magnetic moment µ of an electron in the hydro-
   gen atom in the (a) s state, (b) p state, and (c) d
momentum is L  | L |  | r  p |
state? (Assume that the spin of the electron is
= rpsin  zero.)
= rp Strategy
= rmv — (8.17) The magnetic momentum of the electron is related
Combining these two equations, we have to its orbital angular momentum L. For the hydrogen
   e  L
atom, this quantity is related to the orbital angular
— (8.18)
 2me  quantum number l. The states are given in
In full vector form, this expression is written as spectroscopic notation, which relates a letter (s, p, d,
 etc.) to a quantum number.

    e  L — (8.19) Solution
 2me  The magnitude of the magnetic moment is given in
The negative sign appears because the electron has Equation 8.20:
a negative charge. Notice that the direction of the
magnetic moment of the electron is antiparallel to    e  L
the orbital angular momentum, as shown in Figure  2me 
 e 
8.10(b). In the Bohr model of the atom, the =  2m  l (l  1)
  e

relationship between  and L in Equation 8.19 is
= B l (l  1)
independent of the radius of the orbit.
The magnetic moment µ can also be expressed in (i) For the s state, l = 0 so we have µ = 0 and µ z = 0.
terms of the orbital angular quantum number l. (ii) For the p state, l = 1 and we have
Combining Equation 8.18 and Equation 8.15, the
magnitude of the magnetic moment is

   e  L A hydrogen atom has a magnetic field, so we expect

 2me  the hydrogen atom to interact with an external
magnetic field-such as the push and pull between two
 e 
=  2m  l (l  1) bar magnets. From Force and Torque on a Current
 e Loop, we know that when a current loop interacts

= B l (l  1) — (8.20) with an external magnetic field B , it experiences a
The z-component of the magnetic moment is torque given by
 
  I A  B
WAVE OPTICS

z    e  Lz
 2me   
= B — (8.22)
 e   
=   2m  m where I is the current, A is the area of the loop, 
 e 
is the magnetic moment, and B is the external
= – Bm — (8.21)
magnetic field. This torque acts to rotate the
The quantity µ B is a fundamental unit of

29
 magnetic moment vector of the hydrogen atom to
align with the external magnetic field. Because
mechanical work is done by the external magnetic
field on the hydrogen atom, we can talk about energy
transformations in the atom. The potential energy of
the hydrogen atom associated with this magnetic
interaction is given by Equation 8.23:
 
U    B — (8.23)
If the magnetic moment is antiparallel to the
external magnetic field, the potential energy is large,
but if the magnetic moment is parallel to the field,
the potential energy is small. Work done on the
hydrogen atom to rotate the atom’s magnetic
moment vector in the direction of the external
magnetic field is therefore associated with a drop in
potential energy. The energy of the system is
Figure 8.11 The Zeeman effect refers to the splitting
conserved, however, because a drop in potential
of spectral lines by an external magnetic field. In the
energy produces radiation (the emission of a
left column, the energy splitting occurs due to
photon). These energy transitions are quantized
transitions from the state (n = 2, l = 1) to a lower
because the magnetic moment can point in only
energy state; and in the right column, energy
certain directions.
splitting occurs due to transitions from the state (n
If the external magnetic field points in the positive
= 2, l = 2) to a lower-energy state. The separation of
z-direction, the potential energy associated with the
these lines is proportional to the strength of the
orbital magnetic dipole moment is
external magnetic field.
U()  Bcos 
= z B
= (Bm)B
= mBB — (8.24)
w h e

B
is the Bohr magneton and m is the angular
r e µ

momentum projection quantum number (or magnetic

orbital quantum number), which has the values
m = – l, –l + 1, ..., 0, ..., l – 1, l. — (8.25)
For example, in the l=1 electron state, the total
energy of the electron is split into three distinct
energy levels corresponding to U = – µBB,0,µ BB.
The splitting of energy levels by an external
magnetic field is called the Zeeman effect. Ignoring
the effects of electron spin, transitions from the l =
1 state to a common lower energy state produce
three closely spaced spectral lines (Figure 8.11, left
column). Likewise, transitions from the l = 2 state
produce five closely spaced spectral lines (right
column). The separation of these lines is
proportional to the strength of the external magnetic
field. This effect has many applications. For
example, the splitting of lines in the hydrogen
spectrum of the Sun is used to determine the
strength of the Sun’s magnetic field. Many such
magnetic field measurements can be used to make a buildup (3) :
map of the magnetic activity at the Sun’s surface How Many Possible States? For the hydrogen
called a magnetogram atom, how many possible quantum states corre-

30
spond to the principal number n = 3? What are The max. no. of e– which can be present in a
the energies of these states? principle energy shell is equal to 2n2. No energy
shell in the atoms of known elements posses more
Solution:
than 32 e–.
For a hydrogen atom of a given energy, the number
of allowed states depends on its orbital angular Azimuthal or Subsidiary or Secondary
momentum. However, the total energy depends on Quantum No.(l) : For the given value of n, the l
the principal quantum number only. can have any integral no. ranging from 0 to n – 1
Hence, If n = 3, the allowed values of l are 0, 1, and which informs :
2. (i) The size of orbitals.
If l = 0, m = 0 (1 state). (ii) The shape of orbitals.
If l = 1, m = – 1, 0, + 1 (3 states); (iii) Energy & angular momentum associated with
and if l = 2, m = – 2, – 1, 0, + 1,+ 2 (5 states). that subshell.
In total, there are 1+ 3 + 5 = 9 allowed states. (iv) The value of extra angular momentum which is
Because the total energy depends only on the possess by the electron present in that orbital of
principal quantum number, n = 3, the energy of each particular subshell is known as orbital angular
of these states is
En3 = –E0(1n2) = –13.6eV 9 = – 1.51eV. momenum which is equal to ћ l (l  1) .
So the overall conclusion is that an electron in a
hydrogen atom can occupy many different angular
Magnetic Quantum No.(m) : Since the
momentum states with the very same energy. As the possible no. of 3-dimensional orientations of the
orbital angular momentum increases, the number of electron present in a particular subshell is equal to
the allowed states with the same energy increases. the no. of orbitals present in that subshell. Thus for
any gien subshell no. of possible values of m is equal
The angular momentum orbital quantum number l is to no. of orbitals present in that subshell and the
associated with the orbital angular momentum of the values are – l — 0 — + l.
electron in a hydrogen atom. Thus the part of magnetism which is due to the
Quantum Numbers particular orientation of electron’s orbital w.r.t. the
The quantum no. directly inform the complete address three axes in space.
of an e– while the values of certain physical properties
Spin Quantum No.(s) : Besides the magnetic
of that e– can also be defined indirectly.
effect produced by it’s angular motion the elect.
Quantum Numbers itself has an intrinsic magnetic property due to spin
about is’s own axis. The quantum no. associated with
n l m n this spin has only two possible values +1/2 and –1/2.
The initial three quantum numbers i.e., n, l & m are
findings of Shrodinger’s equation. Spin magnetic moment, m = n(n  2) B.M.

Principle Quantum No.(n) : It tells us about the An additional value of angular momentum, which is
shell in which that elect. resides. Therefore it may an intrinsic property of that electron is known as
have all integral values from 1 to ¥ but only values spin angular momentum of electron. The spin angular
from 1 to 7 have been established in the atoms of momentum of an electron, along any particular
known elements so far. direction, can only take on the values ћ / 2 or
For a given subshell if the value of n ћ / 2 .
increases: We denote the spin of a particle by s and it’ss
(i) It will increase distance of the electron from component along the z-axis by sz. The eigen values
nucleus. of the square of the magnitude of the spin operator
(ii) It will increase the value of energy possess by are s2  s(s  1)ћ2 .
WAVE OPTICS

that electron of the given subshell.

(iii) It will increase the size of orbital of that Pauli’s exclusion principle : It is imposssible for
electron. any two electrons in the same atom to have all the
(iv) It will increase the value of angular momentum quantum no. identical.
posses by that electron.
Electronic configuration
Shell No. Shell Subshell

31
 1 K only s
2 L one s and one p
3 M one s, one p & one d 5 5s 5p 5d

Energy Level
4 N one s, one p, one d & one f 4 4s 4p 4d 4f
5 O one s, one p, one d, one f & one g
3 3s 3p 3d

2 2s 2p
Subshell no. of orbitals
s 1 1 1s
p 3
s p d f
d 5
subshells
f 7
Energy level diagram of subshells
g 9
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s <
4d < 5p < 6s < 4f < 5d < 6p < 7s

buildup (3) : buildup (3) :

Tell the no. of maximum electrons possible in d- Express the electronic configuration of following:
17A ® 1s 2s 2p 3s 3p
i) 2 2 6 2 5
orbital.
23A ® 1s 2s 2p 3s 3p 4s 3d
ii) 2 2 6 2 6 2 3
Sol. 2
Any of the orbital of given subshell has maximum of 2
electrons. eg. s-orbital or d-orbital or f-orbital. Completely fulfilled as well as completely half
filled subshell stability rule :
Subshell maximum no. of electrons possible
Completely fulfilled as well as completely half-filled
s 1´2
state of any subshell has more stability as compared
p 3´2
to any of it’s partially filled state.
d 5´2
f 7´2 The rule does not play any role in case of s-subshell.
9´2
g
buildup (3) :
Express the electronic configuration of following:
29A ® 1s 2s 2p 3s 3p 4s 3d
2 2 6 2 6 1 10
Filling of electrons in the various subshells i)
24A ® 1s 2s 2p 3s 3p 4s 3d
Aufbau principle : Electrons prefer to fill that ii) 2 2 6 2 6 1 5

subshell which has lesser energy when more than one

Any of the d4 as well as d9 configuration present at
subshells of diff. energy are available and the energy
the terminal positions is always converted to its
of any subshell is defined as follows :
completely half-filled or fulfilled state
(n + l) rule : Energy of any subshell is directly
correspondingly by using electron from s-subshell
proportional to (n + l) of that subshell of just lesser energy.
energy subenergy
level level
0 for s
buildup (3) :
equal to Select the incorrect configurations :
shell no. 1 for p
i) ns2 (n – 1) d5
2 for d
ii) ns2 (n – 1) d10
3 for f
iii) ns2 (n – 1) d4
With the help of (n + l) rule, we can arrange the iv) ns2 (n – 1) d9
different subshells in the order of their energy v) ns1 (n – 1) d5
vi) ns1 (n – 1) d10
Sol.
(iii) and (iv) are incorrect while other are correct
which can be explained by Aufbau principle.
Filling of electrons in various orbitals

32
 Hund’s rule : The filling of electrons in the orbitals 16 Determine the electronic transition in Li 2+ ion
of equal energy always occurs in such a manner by emitting lights of wavelength equal to the
which no. of unpaired electrons become maximum k/a wavelength of 2nd Balmer line (n2 = 4 to n1 = 2) of
Hund’s rule. Which can be explained on the basis of He+ ion.
pairing energy. Sol.
Filling of electrons in an orbital:
4  4    9  9 
Pauli’s Exclusion principle : No two elecetrons can 4 16  n12 n22 
be identified by the same set of quantum numbers.
 n1 = 3, n2 = 6
7. Determine the 2nd ionisation energy of He and 3rd 13. A glass bulb has a sample of excited hydrogen. This
ionisation energy of Li. hydrogen is allowed to relax and the light coming
Sol. out is made to incident upon another glass bulb
The ionisation energy of H like species is containing some excited He+ ion. Finally the He+
ions we allowed to return back to their ground
13.6  Z2 eV state. The most energetic photon coming out from
I.E.  He + sample has energy equal to 53.55 eV.
n2
Determine orbit number of excited state of H-atom
2nd I.E. of He = 54.4 eV ( n = 1, Z = 2)
as well as He+ ions.
3rd ionisation of Li is
The energy released in transition of H = Transition
IE = 122.4 eV ( n = 1, Z = 3) energy in He+.
12. Determine the shortest and the longest wavelength Also, most energetic photons would be emitted from
of transition in Lyman series of a H-atom. He+ sample when the electron comes from the highest
Sol. orbit to ground state.
The Rydberg’s formul
a for a H-atom, applicable to Lyman series is

 53.55 eV = 13.6 × 4 1  12
n 
 n = 8 = Highest orbit number in He+
1  R 1  1  Now equating the transition energy of H and He+ as
H where, n = 2, 3, 4, .....
  n2 
13.6 1  12   13.6  4  12  12 
For shortest  means
1
has to be maximum and it  n1   n2 8 
  n1 = 4 and n2 = 2, i.e., H has electron in the fourth
will occur at maximum value of n, i.e. at n = . orbit He+ has electrons in second orbit initially.

min  1  1  R  14. Bond energy of H2 is 436 kJ/mol. Determine the

  min H longest wavelength of photons which when made
RH 
to incident upon a sample of hydrogen gas (H2) will
1 bring about photochemical atomisation (free
= m 1
1.0973  107 radical formation) followed by excitation to third
= 91.13 × 10–9 m Bohr’s orbit.
436  103
1 Bond energy per molecule =
For longest  means has to be minimum and it 6.023  1023

will occur at minimum value of n, i.e. at n = 2. = 7.24  1019 J


1  R 1  1
max H
 4
Excitation energy/H atom  2.18  1018 1  J
1
9 
–18
= 1.93 × 10 J
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In the process of decomposition one photon breaks one

 max  4
3R H covalent bond and then excites two H-atoms to the third
orbit as
= 121.51 × 10–9 m
 Energy of photon = BE + 2 × Excitation energy
= 121.51 nm = 7.24 × 10–19 J + 2 × 1.93 × 10–18 J
= 4.584 × 10–18 J

33
 hc  6.625  1034  3  108
 
E 4.584  1018
–9
= 43.3 × 10 m = 43.3 nm
15. Which first transition in He+ would emit light in
visible region that is also present in the emission
spectrum of H-atom.
Balmer lines of H-atoms lies in the visible region for
which the wavelength is determined as
1 R 1 1
 H 
4 n2 
The same should be the wavelength of first line of He+


1R 1 1
 H
4 n2 
 R H  42  42  He
 n1 n2 
 n1 = 4, n2 = 6 ( n = 3)
17. Calculate the circumference of fifth Bohr orbit of
an electron whose de-Broglie wavelength
corresponds to translational kinetic energy of H
gasesous atom at 27°C.
3 p2
Translational kinetic energy  2 kT  2m
e

 p  3kTme : k  Boltzman's constant (R/N A )

Circumference = 2r = n
nh nh
= p  3kTm
e

 5  6.625  1034
[3  1.38  1023  300  9.1  1031]1/2
= 31.16 × 10–9 m
= 31.16 nm

34