Atomic structure

Atom
• The word atom has been derived from Greek word (a= absence , tomos = cut)which
means indivisible or uncuttable.
• Atom is the smallest particle that take part in chemical reaction.
• The concept of atom for the first time was put forward by an English chemist John Dalton
in 1808, which is known as Dalton’s atomic theory.
• Atom consist of three fundamental particles i.e. electron , proton , and neutron.
 Electron
Discovered by Joseph John Thomson in 1879 as a result of discharge tube
experiment. In this experiment a gas is filled in a specially designed tube provided with metal
electrodes and passed high voltage electricity at low pressure through the tube. It is observed
that some rays are started to flow from cathode towards anode which are called cathode rays.
Properties of cathode rays are:
1. Cathode rays are a stream of negatively charged particles
2. They travel in a straight line.
3. They are deflected by electric and magnetic field towards the anode.
4. They produce a heating effect when they strike metal foil.
5. They have the property to ionize the gas through which they pass
Later on, it was found that cathode rays are nothing but a stream of an electron. Thus an
electron is a negatively charged particles having a unit negative charge and mass is equal to
1/1837 of a hydrogen atom.
Mass of electron = 9.09 x 10-28 gm.
charge on electron = -1.602 x 10 -19 coulomb
 proton
Proton was discovered by E. Goldstein in 1886 through an anode ray discharge
tube experiment. On passing high voltage through discharge tube filled with hydrogen gas
at low pressure and provided with perforated cathode it was observed that some rays
travel opposite of cathode rays i.e. travel towards cathode which are called anode rays or
positive rays
 Properties of anode rays are:
i. They consist of positively charged particles.
ii. They travel in a straight line.
iii. They are deflected by electric and magnetic field towards the cathode.
iv. They cause a heating effect.
The above observation concludes that anode rays are positively charged and named by
Goldstein as protons.
Thus, a proton is a positively charged particles having a unit positive charge and mass
equal to that of a hydrogen atom.
Mass of proton = 1.67 x 10-24 gm.
charge = + 1.602 x10 -19 coulombs
 Neutron
Neutron is discovered by James Chadwick in 1932 by bombarding α - particles on a thin
sheet of beryllium. A highly penetrating neutral particle was observed called a neutron.
Thus a neutron is an electrically neutral particle having a mass nearly equal to that of a
hydrogen atom. Mass of neutron=1.67 x 10-24 gm.

He4 + Be9 C12 + n1 (neutron)

2 4 6 0
 + α ( 2He 4
n –p= 134-84 = 50 N-p=132-82 =50
 Atomic models
Different types of atomic models were purposed , some of the important and significant models
are described below;
1. Thomson’s atomic model (plum pudding model or watermelon model of an atom)
according to J.J Thomson (1898) an atom is positively charged sphere of radius 10 -10 m.
according to this model an atom consist of sphere of positive charge in which negatively charged
electrons are embedded like seeds in the watermelon (or raisin in the pudding) . So this model is called
plum pudding model or watermelon model. Total positive charge in the atom is equal to the total negative
charge. This maintains the electrical neutrality.

Fig: Thomson’s atomic model

Limitations
1. only few properties of an atom can be understood.
2. This model could not explain the origin of the spectral lines in hydrogen atom .
 Rutherford's atomic model (alpha particle scattering experiment)
Ernest Rutherford and his co-worker(Geiger and Marsden) carried out the
alpha rays scattering experiment in 1911 to determine the structure of an atom.
In this experiment, he bombarded α- alpha particles (positive particles
equal to He++ ion) emitted from a radioactive substance(polonium) on a very thin gold
foil (0.0004cm thickness). Lead can absorb alpha particles. So lead plate with a slit was
used to obtain a beam of alpha particles. α-paricles produces tiny flashes on circular zinc
sulphide screen which were observed by movable microscope as shown in fig; below
Movable microscope

Zns screen
few
Very few

most

Fig: Rutherford α-scattering experiment

 observations;
Following observations were made on the basis of alpha scattering experiment
• Most of the alpha particles passed through the gold foil without deflection.
• Some of the alpha particles deflected through small angles.
• Very few alpha particles were deflected through angles more than 90° or bounced back.
Inferences
On the basis of above observations following conclusions were made
i. Most of the α-particles passed through the gold foil without getting deflected, it
indicates most of the space inside the atom is void or empty.
ii. The cause of deflection of α- particles through small angle is due to the presence
of heavy positively charged body at the center of an atom . This is due to the fact
that positively charged center repels positive particles (i.e α- particles)
iii. The diameter of center of an atom (10 -13 cm)is very small in comparison to the
diameter of an atom(10 -8 cm) . That is why very few rays are reflected back due to
the close encounter with the center of an atom . Or it can be said that whole mass
of an atom is concentrated at the nucleus.
Fig : Scattering of α- particles by a single atom
 On the basis of above conclusion Rutherford purposed a nuclear model to an atom called
as Rutherford’s nuclear model of an atom. The postulates of this model are as follows;
i. An atom consists of a positively charged nucleus (radius 10 -13 cm or 1 Fermi) at which
the entire mass is concentrated and its size is extremely small as compared to the size
of the atom (radius 10 -8 cm).
ii. most part of atom is void or empty.
iii. The atom is electrically neutral since the no. of electrons is equal to number of
positive charge in the nucleus
iv. Electrons and protons are held together by means of electrostatic force of attraction
v. The centrifugal force of the revolving electron is balanced by the electrostatic force of
attraction between the electron and nucleus.

fig ;(a)Rutherford nuclear

model of an atom
Fig: (b) revolution of (a)
electron around the nucleus (b)
Limitations of Rutherford atomic model
i. It could not explain the stability of an atom:
According to the electromagnetic theory purposed by Maxwell, any rotating charged
particles should lose energy continuously by emitting radiation and follows spiral path and
ultimately should falls into the nucleus. The atom should thus collapse. But this could not
happen because an atom is stable in nature.

Fig: moving electron follows a spiral path

ii. It can not explain the origin of line spectra of atoms;
According to Rutherford atomic model, electron revolving around the nucleus is
expected to emit continuous energy spectrum .But atom such Hydrogen emits
line spectra which are discontinuous.
 Bohr's atomic model
In 1913, Neil Bohr proposed an atomic model to overcome the limitations of Rutherford's atomic model of
the atom. He applied quantum theory of radiation developed by Plank and Einstein to explain stability of
atom and origin of atomic spectra. The postulates of Bohr's atomic model are:
i. Electrons in an atom revolve around the nucleus in a definite circular path called orbits or shells.
ii. Each orbit is associated with definite energy and electron holding capacity. The different orbits are
represented by letter ‘n’ and ‘n’ can have values of 1,2,3,4….etc. and represented by K,L,M,N etc. from
center to outward.
Value of n 1 2 3 4
shell k L M N
iii. The energy of an orbit increases with increasing distance from the nucleus . The increasing energy order
of orbit is
E1<E2<E3<E4 … etc.
The energy difference between two regular orbit is equal to one quantum
i.e. E2 – E1 = h ν { E1 = energy of 1st orbit & E2 = energy of 2nd orbit)
or ∆E = h ν Where h = plank’s constant & ν = frequency of radiation (nu)
But the successive energy difference between orbit goes on decreasing on moving away from the nucleus .
i.e. E2- E1 > E3-E2 > E4-E3> ….
 n=
E1
E2
E3

Fig ; Bohr’s atomic model

iv. The maximum number of electron that an orbit can accommodate is calculated by Bohr –Burry rule i.e
2n2 rule . Where n is the number of orbit .
For 1st orbit ; n= 1 (k shell)
2n2 = 2 x12 = 2 i.e first orbit can hold 2 electrons .
For 2nd orbit ; n= 2 ( L –shell)
2n2 = 2x 2 2 = 8 i.e 2nd orbit can hold maximum of 8 electrons and so on
v. As long as an electron remains in a particular orbit, it will neither gain nor emit (lose) energy and hence
the energy of the electron in a particular orbit remains constant. This means these orbits are non-radiating
and thus called stationary state or energy level . This explain the stability of an atom.
vi. Energy is emitted or absorbed by the electron in the form of a photon only when it jumps
from one energy level to another. The quantum or photon of energy absorbed or emitted is
the difference between the higher and lower energy level. ∆E = E2 – E1 = hv
∆E = energy emitted or absorbed
E2 = higher energy level Energy absorbed Energy emitted
E2 E2
El = lower energy level
E1 E1
h = Plank's constant
v= frequency of radiation + +

Fig: Absorption of Fig : emission of radiation (de-excitation)

radiation (excitation)
Energy is absorbed when an electron jumps from lower to higher energy level and energy is
emitted when an electron jumps from higher to lower energy level. The lowest energy state of an
atom is known as ground state.
The absorption and emission always occur in whole number of quanta thus no any electron can
exist in between two orbits. This behavior of electrons is responsible for absorption and
emission spectra of atoms
vii. The centrifugal force acting on moving electron is balanced by attractive force
between nucleus and electron i.e. centripetal force

viii. Only those orbits are permitted in an atom where angular momentum of electron is
equal to integral multiple of h/2π. i.e
𝑛ℎ
Angular momentum =
2π
𝑛ℎ
Or, mvr =
2π
Where , m= mass of electron
v = velocity of electron
r= radius of orbit
n= positive whole number
h = plank’s constant.
Hence the energy as well as angular momentum of electron is quantized.
Atomic spectra;
The electrons in an atom may absorb or radiate energy of certain wavelength which can
be recorded in the form of bands or lines called as atomic spectra. There are two types of
atomic spectra
a. Absorption spectra ;
When an atom in its vapour state is placed in white light it absorbs light of characteristic
wavelength due to the presence of electron in it. The light of other wavelength gets
transmitted . This behavior of atoms produces a series of dark lines on white background
called as atomic absorption spectra.
b. Emission spectra
When an atom in its vapour state is heated to high temperature , the electrons undergo
in excited state . When heating is stopped , the atoms return in ground state by emission
of certain wavelength. The emitted radiation produces a series of bright lines on dark
background , called as emission spectra. Hydrogen atom form such spectra.
Explanation of hydrogen spectra on the basis of Bohr’s atomic model
When an electric discharge is passed through hydrogen gas filled in a discharge tube at low
pressure , the molecules of hydrogen breaks into atoms . These atoms absorb energy from
electric spark . As a result the electrons in the ground state jump to higher energy levels,
2,3,4,5….etc. depending upon the amount of energy absorbed by atoms of hydrogen. But
the excited electrons at higher energy levels are unstable . So they return back to the lower
energy state or even to the lowest energy level i.e. ground state after a very short interval
of time. At the time of returning back to lower energy level they emit energy in the form of
radiation. Which give rise to line spectra. The wavelength of emitted radiation depends
upon the energy difference between higher and lower energy level.

Following calculation give the magnitude of wavelength for the electron moving from
higher level to lower level
1 1 1
=R{ - } where, λ = wavelength of radiation
λ 𝑛12 𝑛 22
R = Rydberg’s constant (R = 1.09 x 10 5 cm-1)
n1 = lower energy level
n2 = higher energy level
The electronic transition which produce different series of spectral lines in hydrogen spectra are
shown as below

Fig : origin of line spectra of hydrogen

 Depending upon the wavelength of radiation emitted , different types of spectral lines
were observed as follows;
i. Lyman series ; the various spectral lines of this series are obtained when an excited
electrons returns from higher energy level to the ground state. Thus for Lyman series n1 =
1 & n2 = 2, 3, 4,5……….∞. The spectral lines of this series lies on ultraviolet region having
wavelength range (950 – 1200) A
ii. Balmer series ; The various spectral lines of this series are obtained when an excited
electron returns from higher energy level to the 2nd energy level. Thus for Balmar series
n1 = 2 & n2 = 3, 4, 5 , 6…… ∞. The spectral lines of this series lies in visible region (λ= 4000
– 6500 A )
iii. Paschen series; The various spectral lines of this series are obtained when an excited
electron returns from higher energy level to the third energy level . Thus for Paschen
series n1 = 3 & n2 = 4, 5, 6……∞. The spectral lines of this series lies in infrared region (λ =
9500 – 18750 A)
iv. Bracket series ; The various spectral lines of this series are obtained when excited
electrons from higher energy level to the fourth energy level. Thus for Bracket series n1 =
4 and n2 = 5,6,7,…..∞. The spectral lines of this series lies in infrared region (λ= 19450 –
40500 A)
v. Pfund series ; the various spectral lines of this series are obtained when electron from
higher energy level returns to the fifth energy level . Thus for this series n1 = 5 & n2 = 6,
7,8…..∞. The spectral lines of this series lies in far infrared region (λ = 37400 -40500A)
vi. Humphreys series ; The various spectral lines of this series are obtained when electron
from higher energy level return back to the sixth energy level. Thus for this series n1 = 6
& n2 = 7,8,9…∞. The spectral lines of this series lies in far IR region ( above 40,500 A)
 Significances of Bohr's atomic model
• It explains the stability of the atom.
• It explains the origin of line spectra of the hydrogen atom.
• It derived the relation to calculate the energy and radii of permissible orbit in hydrogen or single
electro system . The expression for energy of electron in nth orbit is
−2π2𝑚𝑒4 −13.6
En = 2 2 = ev/atom
𝑛ℎ 𝑛2
And radius of the nth orbit of hydrogen atom or hydrogen like system is
𝑛2ℎ2
rn = 2 2
4π 𝑚𝑒
Where m is mass, e is charge of electron , h is Plank’s constant and n is the principal quantum
number, n= 1, 2, 3,4,…so on.
Limitations of Bohr's atomic model
i. No explanation for the spectra of multi-electron system: This model only explained the origin
of spectra of the hydrogen atom and hydrogen-like ions like He+, Li++, etc. but it doesn't explain
the origin of the spectra of the multi-electron system.
ii. No explanation of the hyperfine structure of spectra: When the hydrogen spectra are
observed with the help of a spectroscope of high resolving power, it is found that the individual
spectral lines are not really single but consists of several closely packed lines called hyperfine
lines. These fine lines cannot be explained by this model. Such structure means that in a given
orbit, there are several orbits called sub orbits having different energies.
iii. No explanation of Zeeman and Stark effect: The splitting of spectral lines into a group
of finer lines in presence of a magnetic field is called the Zeeman effect and the
splitting of spectral lines in presence of an electric field is called the Stark effect. Bohr's
atomic model didn't explain such effects.
iv. No explanation for the dual nature of electron ( de- Broglie equation) : This model has
treated electron as a particle of a certain mass revolving around the nucleus in a fixed
orbit. But de-Broglie suggested that electron has a dual nature i. e. electron behaves as
a particle as well as wave nature.
v. This theory is against Heisenberg's uncertainty principle; According to Bohr , an
electron is revolving in a circular orbit around the nucleus situated at fixed distance
from nucleus with definite velocity. This postulate is against Heisenberg's uncertainty
principle which states that “It is impossible to determine simultaneously the exact
position and exact velocity or momentum of microscopic moving particle like electron,
proton neutron etc.’’
vi. This theory can not explain the movement of electron in three dimensional space.
Dual nature of electron (de-Broglie equation)
In 1905, Einstein suggested the dual nature of light According to this, light possesses a
wave and particle nature. In 1924, de Broglie advanced the idea that not only photons or
light but also matter like electron shows the dual nature. The wave associated with
matter is the matter wave or de-Broglie wave. So, the electron is a subatomic particle that
can behave sometimes as a particle and sometimes as a wave.
de- Broglie was able to obtain the mathematical relationship between wavelength
and momentum with the help of Plank’s theory and Einstein's theory of relativity.
According to Plank's theory energy of photon can be calculated by using the relation;
E = hv - --(i)
where, E = energy of photon,
h = Planck's constant
v= frequency
According to Einstein equation,
E = mc2 —- (ii) where, m=mass, c=velocity of light
Equating equation (i) & (ii)
hv = mc2 ( ν = c/λ)
𝑐
Or, h = mc2
λ
ℎ
Or, = mc
λ
For material particle like electron having mass m and velocity v above equation can be
written as λ α
𝟏
𝒎
ℎ
Or, λ = ……. (iii) i.e.
𝑚𝑐
ℎ
Or, mass x velocity =
𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ (λ)
ℎ
Or, momentum (p) =
λ
ℎ 𝟏
0r, λ = ……………..(iv) :. λα
𝒑
𝑝

Equation (iii) and (iv) are called de – Broglie equation. The wavelength of electron can be
calculated by using above equations. Where λ is called de- Broglie wavelength and is
inversely proportional to mass of particle. For microscopic particle λ is large and for
macroscopic particle λ is large.so λ of macroscopic particle can not measured . Hence
wave character is significant only for microscopic particle like electron.
Significance of de – Broglie equation
i. It shows the relation between particle and wave character of matter.
ii. It is applicable for all matter but more significant for microscopic particles like electron.
iii. It helps to deduce Bohr’s condition for quantization of angular momentum.
• A particle occupies a particular space. e.g.. a pen occupies a particular space.
• A wave spreads in space. e.g.. sound of mike reaches everywhere.
• No two or more particles occupy the same space at the same time.
• Two or more wave co-exists in the same region at the same time.
• When many particles are in space, the total volume is equal to the sum of their
volume.
• When many waves are present, the resultant wave can be greater or smaller than
each individual wave.
Heisenberg uncertainty principle
It states that “It is impossible to determine the position and momentum of microscopic
particles like an electron simultaneously and accurately".
Mathematically,
if ∆𝑥 𝑎𝑛𝑑 ∆𝑝 are the uncertainties in the measurement of position and momentum of
subatomic particle like electron. Then according to this principle
ℎ
∆𝑥. ∆𝑝≥
2π
This relation is called uncertainty relation . From this relation it can be said that if position
of a particle is measured accurately i.e.∆𝑥 = 0 then the momentum or velocity will be
measured less accurately and vice- versa.
Hence uncertainty principle suggest that in an atom , an electron does not always remain
at a fixed distance from the nucleus . It keeps moving in whole space around the nucleus
, but tends to remain most of the time within a small volume around the nucleus where
the probability of finding electron is maximum.
 Differences between orbit and orbitals
Orbit Orbitals
i. It is a well defined circular path (or i. It is the region or space around the
shell) of revolving electron around nucleus of atom where probability of
the nucleus. finding electron is maximum
ii. An orbit has got fixed radius ii. The radius of an orbital is not fixed.
iii. Orbits are denoted with symbols K, L iii. Orbitals are denoted with symbols
, M, N etc. or numerals 1,2,3,4 etc. s,p,d ,f etc.
iv. There may be infinite number of iv. There are many types of an orbitals
orbits in an atom in an atom
v. An orbit represents the movement v. An orbital represents the movement
of electron in one plane. of electron in three dimensional
vi. Orbits are non-directional in nature space.
hence they can not explain the vi. Orbitals are directional in nature and
shape of molecules. hence they can account for the
vii. an orbit can hold maximum of 2n2 shape of molecules.
electron where n is the number of vii. An orbital can hold maximum of 2
orbits. electrons with opposite spins.
Shape of s and p – atomic orbitals
Shape of s- orbital
S-orbital is spherically symmetrical in shape . Therefore probability of finding electron in
all direction from the nucleus is same.
The size and energy of s- orbital increases with increasing value of n (principal quantum
number)
Shape of p- orbital
There are three types of p- orbitals; px, py & pz. Each p- orbital has two lobes symmetrical
about particular axis. These two lobes (dumb- bell shape) touch each other at the origin
there is zero electron density.
Px orbital is oriented towards x- axis and symmetrical along this direction .
Py orbital is oriented towards Y- axis and symmetrical along this direction.
Pz orbital is oriented towards Z- axis and symmetrical along this direction.

The orbitals belonging

to the same sub- shell
are called degenerate
orbitals they have same
energy. P- orbital possess
three degenerate
orbitals they are px, py
and pz. They have
different orientations.
 Quantum numbers
The quantum mechanical parameters which tell us about the location and motion of an
electron in an atom are called quantum numbers. It gives complete information of a
particular electron relating to its energy level, shape and orientation of orbital with its
spin. The four quantum numbers required for characterization of electron are as follows ;
I. Principal quantum number (n)
II. Azimuthal or subsidiary quantum number(l)
III. Magnetic quantum number (m)
IV. Spin quantum number(s)
I. Principal quantum number (n)
It was introduced by Bohr.
It represents the number of shells or orbit or energy level in an atom to which the electron
belongs.
It is denoted by letter n. it can have only positive integer values starting from 1 to ∞.
Information given by principal quantum number are
• The value of n represents the shell or orbit to which the electron belongs.
Principal quantum number (n) Orbit or shell or energy level
1 1st or K
2 2nd or L
3 3rd or M
4 4th or N

• The value of n gives the maximum number of electron that can hold by a shell. It is
given by the formula 2n2 (Bohr Bury rule)
If n= 1( k -shell) 2n2 = 2x 1 2 = 2 i. e K shell can hold maximum of 2 electrons
If n= 2 (L-shell) 2n2 = 2x2 2 = 8 , i.e L-shell can hold maximum of 8 electron.
If n= 3(M-shell) 2n2 = 2x32 = 18 , i.e. M-shell cn hold maximum of 18 electrons and
so on.
• The value of n determines the energy of electron in a given shell. According
to Bohr’s calculation energy of electron of hydrogen or hydrogen like ions
are given by
−2π2𝑚𝑒4
En =
𝑛2ℎ2
Where En = energy of electron in nth orbit.
m= mass of electron
e= electronic charge
n= principal quantum number
h = plank’s constant
Higher the value of n higher will be the energy of electron.
• Value of n determines the distance of electron from the nucleus. More the
value of n more far is the electron from the nucleus.
II. Azimuthal or subsidiary quantum number (l)
It was introduced by Sommer Field. This quantum number is able to explain the
appearance of a group closely spaced lines (fine lines) seen in hydrogen spectrum
It is denoted by letter ‘l’ and depends upon the value of ‘n’ and hence this quantum
number represents the sub-shell of given shell.
For the given value of ‘n’ l can have values from 0 to (n-1)
Information given by azimuthal quantum number areas follows
• Different values of l represents different sub- shells denoted by small letters s,p,d&f
These letters are taken from the short form of sharp (s), principal(p), diffuse (d) and
fundamental (f)
Value of l Letter for sub- shell
0 s
1 p
2 d
3 f
• It helps to calculate total number of sub- shell and no, of orbitals in a main shell.

Value of n Value of l [ zero to (n-1)] No. of sub –shell = n

1 0 1 (1s)
2 0,1 2 (2s, 2p)
3 0,1,2 3(3s,3pand 3d)
4 0, 1,2,3 4 (4s, 4p, 4d and 4f)

• It helps to calculate the total number of electron that can hold by a sub- shell. It is given by the formula
2 (2l +1).

Sub- shells Value of l Total no. of electron 2(2l +1)

S 0 2
P 1 6
d 2 10
F 3 14

• l values is a measure of angular momentum of electron while moving round the nucleus . That is why this
quantum number is also called angular momentum quantum number
III. Magnetic quantum number (m)
It was introduced by Lande and Zeeman
It is denoted by letter ‘m’. It represents the sub- division of sub- shells called as orbitals
.the value of m depends upon the value of l given by the formula m= -l to +l including
zero.
This quantum number has been introduced to explain Zeeman and stark effect.
Information given by magnetic quantum numbers are as follows;
• It gives the number of orbitals in a given sub- shell and determines the orientation of
orbital in space.
Sub- shell Value of l Value of m (-l to +l) N0. of orbitals (2l +1)
s 0 0 1
p 1 -1, 0, +1 3
d 2 -2,-1, 0, +1, +2 5
f 3 -3, -2, -1,0,+1,+2,+3 7

• Total no. of orbitals in a main shell is equal to the total no. of m values for the given
value of l. for the given value of n , total no. of orbitals are given by formula n2
Value of n Value of l {0 to (n-1)} Value of m (-l to +l) Total no. of orbitals (n2)
1 0 (s) 0 1
2 0(s) O 4
1(p) -1, o, +1
3 O(s) O 9
1(p) -1, o +1

2(d) -2, -1, o, +1, +2

4 o(s) 0 16

1(p) -1 ,0,+1

2(d) -2,-1,0, +1, +2

3(f) -3,-2,-1, 0, +1, +2, +3

Above tabulation shows that s orbital posses only one orientation, p- orbital posses three orientation, d- orbital
posses five orientation and f- orbital posses seven orientations.
 IV. Spin quantum number(s)
It was introduced by Goldsmith and Ulhenbeck. It is denoted by letter ‘s’. An electron in
an orbital performs two types of motion i.e. revolution around nucleus and rotation
about its own axis . The rotation of electron is called as spinning of electron which is
described by spin quantum number.
It represents spinning motion of an electron about its own axis in a given orbital.
s can have only two values i.e. +1/2 and -1/2, which corresponds to clockwise and
anticlockwise spin respectively.
s= +1/2 clockwise spin (↑)
s= -1/2 anticlockwise spin (↓)
The two electrons in an orbital always perform opposite spins.

Clockwise
Anti- clockwise spin
spin
 Rules for filling electrons in atomic orbitals
1. Bohr Bury rule
The rule which governs distribution of electrons in different shells is called Bohr Bury rule
which are as follows;
1. The maximum number of electron in shell is equal to 2n2. where n= principal quantum
number.
If n= 1( k -shell) 2n2 = 2x 1 2 = 2 i. e K shell can hold maximum of 2 electrons
If n= 2 (L-shell) 2n2 = 2x2 2 = 8 , i.e L-shell can hold maximum of 8 electron.
If n= 3(M-shell) 2n2 = 2x32 = 18 , i.e. M-shell cn hold maximum of 18 electrons and
so on.
2. The outermost orbit and second last orbit cannot have more than 8 and 18 electrons
respectively.
3. Electrons may go into a new outer shell although the inner shells are incompletely filled.
4. Even if the capacity of penultimate shell exceeds 8 , it can not have more than 8 electrons
unless there are 2 electrons in outermost shell. And it can not have more than 9 electrons
unless the ante- penultimate shell is completely filled. In such cases , the outermost shell can
have more than 2 electrons only after there are 18 electrons in the penultimate shell.
2. Aufbau principle
Aufbau (German word) means building up or construction.
This principle is mainly concerned with distribution of electrons in different sub- shells of
an atom. This principle states that “ The orbitals are filled up with electrons in the
increasing order of their energy”
OR
“the orbitals f minimum energy are filled first with electrons and then orbitals of higher
energy start to fill.”
The sequence of filling of various sub- shell can be obtained from the following diagram;
Fig; sequence of filling various sub- shell

The increasing order of energy of various sub- shell can be taken from above diagram is as follows
1s< 2s < 2p < 3s< 3p< 4s < 3d<4p< 5s< 4d< 5p< 6s< 4f< 5d< 6p<7s < 5f< 6d<7p<8s
The energy of orbital depend upon the principal quantum number(n) and Azimuthal
quantum number(l)
The above sequence can be justified by Medlung’s rule which is also called (n+ l) rule.
According to this rule
The orbitals with lower value of (n+ l) has than the orbitals of higher (n+l) value. lower
energy
For example 4s orbital is filled before 3d because (n+l) value for 4s is lower than that of
3d orbital
for 4s orbital For 3d orbital
n= 3, l= 2
n= 4, l= 0 n+l = 3+2 = 5
n+l = 4+ 0 =4
When two orbitals have same (n+l) value, the orbital with lower value of n is lower in
energy .for example ; 3d and 4p orbital have same (n+l) values but 3d is filled before 4p
because value of n for 3d is lower than that for 4p.
for 3d ; n= 3, l= 2 (n+l) = 3+2 = 5
for 4p ; n= 4, l=1 (n+l) = 4+1 = 5
 Limitations of Aufbau principle
The electronic configuration of some element is different from that suggested by Aufbau
principle. This is due to extra stability provided by half filled and completely filled orbitals
than partially filled orbitals.
Exactly half filled and completely filled orbitals have greater stability than other due to
following reasons:
1. Symmetry: Half filled and full filled orbitals are more symmetrical than any other and
symmetry lead to stability
2. Exchange energy:
The electrons present in different orbitals of the same subshell can exchange their position.
Each such exchange leads to a decrease in energy known as exchange energy. Greater the
number of exchanges, the greater the exchange energy and the greater the stability.
Examples ; electronic configuration of
Cr ; 1s2, 2s2, 2p6, 3s2, 3p6, 4s1 , 3d5
Cu ; 1s2, 2s2 , 2p6, 3s2, 3p6 , 4s1, 3d10
Ag; [Kr] 5s1 , 4d10
 Pauli’s exclusion principle
(given by Wolfgang pauli in 1952)
Pauli’s exclusion principle states that ‘ no any two electron in an atom can have same values for all
the four quantum numbers’
This principle is very useful in constructing electronic configuration of atoms in orbital levels.
According to this principle if three quantum numbers for two electrons in an atom are identical ,
the fourth quantum number should be different.
Illustration
Let us consider Helium atom which has two electrons . The four quantum numbers for these
electrons are as follows;
Electrons quantum numbers

n l m s
1st electron 1 0 O +1/2
2nd electron 1 0 0 -1/2
The electronic configuration of Helium atom is 1s2. two electron of helium atom possess same
values of n,l & m but different values of s, because one electron moves clockwise and another
anticlockwise. According to this principle, opposite spins of electrons in an orbital make the
electronic configuration more stable than that of parallel spin or same spin.
Hund’s rule of maximum multiplicity
This is the rule for filling degenerate orbitals with electrons in an atom. This rule states
that ‘ when the electrons fill up in a sub – shell having more than orbitals, each orbital is
filled up first by single electron with same spin followed by pairing with opposite spin.’
This means pairing of electrons will not occur in any orbital(degenerate orbitals) unless all
the available orbital have one electron in each.
Illustration
Correct
Electronic configuration of oxygen is ; 1s2 , 2s2, 2p4 way
i.e. 1s2 ,2s2 ,2px2 ,2py1, 2pz1 1s 2s 2px 2py 2pz
but not 1s2, 2s2, 2px2, 2py2,2pz0 ↑↓ ↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑↓ ↑↓
Incorrect way
Similarly electronic configuration of nitrogen is 1s2 , 2s2 , 2p3
↑↓ ↑
↑ ↑ ↑
2px 2py 2pz 2px 2py 2pz
Correct way incorrect way
Electronic configuration of elements in ground state
Electronic configuration of ions