CLASS XI

CHEMISTRY
UNIT – 2
QUANTUM MECHANICAL
MODEL OF ATOM
This unit is about:
Bohr’s atomic model and its limitations,
Wave particle duality (i.e.)De-broglie
wavelength,
Quantisation of angular momentum,
Davisson and Germer experiment,
Heisenberg’s uncertainty principle,
Schrodinger equation,
Main features of quantum mechanical
model of atom,
Quantum numbers and its types,
Shape and Energies of atomic orbitals,
Aufbau principle,
Pauli’s exclusion principle,
Hund’s rule

History of Atomic models:

All the things are made up of matter and the basic unit
of all matter is ATOM.
Atom derived from Greek word ‘a-tomio’ means ‘non-
divisible’.
Atom was considered as non divisible until the
discovery of sub atomic particles such as electron, proton
and neutron.
J.J.Thomson’s cathode ray experiment – atoms consist
of –vely charged particle called ‘electrons’.
Atoms are +vely charged sphere in which the
electrons are embedded like the seeds in watermelon.
Later Rutherford’s α-ray scattering experiment results proved
that Thomson’s model was wrong.
Rutherford bombarded a thin gold foil with a stream of fast
moving α-particles.
It was observed that
(i) most of the α–particles passed through the foil.
(ii) some of them were deflected through a small angle and
(iii) very few α–particles were reflected back by 180°.
He proposed that in an atom there is a tiny positively
charged nucleus and the electrons are moving around the
nucleus with high speed.
The theory of electromagnetic radiation states that a
moving charged particle should continuously loose its
energy in the form of radiation.
Therefore, the moving electron in an atom should
continuously loose its energy and finally collide with
nucleus resulting in the collapse of the atom.
However, this doesn't happen and the atoms are stable.
Moreover, this model does not explain the distribution of
electrons around the nucleus and their energies.
Bohr atom model:
The work of Planck and Einstein showed that the
energy of electromagnetic radiation is quantised in
units of hν (where ν is the frequency of radiation and
h is Planck's constant 6.626 × 10-34 Js).

Extending Planck’s quantum hypothesis to the

energies of atoms, Niels Bohr proposed a new atomic
model for the hydrogen atom.
This model is based on the following
assumptions:

1. The energies of electrons in an atom are

quantised.
2. The electron is revolving around the nucleus in a
certain circular path of fixed energy called
stationary orbit.
3. Electron can revolve only in those orbits in which
the angular momentum (mvr) of the electron must
be equal to an integral multiple of h/2π.
i.e. mvr = nh/2π -------- (2.1)
where n = 1,2,3,...etc.,
4. As long as an electron revolves in the fixed
stationary orbit, it doesn’t lose its energy. E2
However, when an electron jumps from
higher energy state (E2) to a lower energy
state (E1), the excess energy is emitted as
radiation. The frequency of the emitted
radiation is

E2 – E1 = hν and

ν =(E2 – E1) -------- (2.2) E1

h

Conversely, when suitable energy is supplied

to an electron, it will jump from lower
energy orbit to a higher energy orbit.
Applying Bohr’s postulates to a hydrogen like atom
(one electron species such as H, He+ and Li2+ etc..) the
radius of the nth orbit and the energy of the electron
revolving in the nth orbit were derived.
The results are as follows:
Limitation of Bohr's atom model:
This model is applicable only to species having
one electron such as hydrogen, Li2+ etc... and not
applicable to multi electron atoms.
It was unable to explain the splitting of spectral
lines in the presence of magnetic field (Zeeman
effect) or an electric field (Stark effect).
Unable to explain why the electron is restricted to
revolve around the nucleus in a fixed orbit in which
the angular momentum of the electron is equal to
nh/2π and a logical answer for this, was provided by
Louis de Broglie.
Quantisation of angular momentum and
de Broglie concept:
According to the de Broglie concept, the electron
that revolves around the nucleus exhibits both
particle and wave character.
In order for the electron wave to exist in phase,
the circumference of the orbit should be an integral
multiple of the wavelength of the electron wave.
Otherwise, the electron wave is out of phase.
Circumference of the orbit = nλ
2πr = nλ ------------(1) [since λ = h / mv]
2πr = nh/mv
Rearranging,
mvr = nh/2π ----------(2)
Angular momentum = nh/2π
The above equation was already predicted by Bohr.
Hence, De Broglie and Bohr’s concepts are in
agreement with each other.
Davisson and Germer Experiment
The wave nature of electron was experimentally
confirmed by Davisson and Germer.
They allowed the accelerated beam of electrons
to fall on a nickel crystal and recorded the
diffraction pattern.
The resultant diffraction pattern is similar to the
x-ray diffraction pattern.
The finding of wave nature of electron leads to
the development of various experimental
techniques such as electron microscope, low
energy electron diffraction etc...
 Heisenberg’s uncertainty principle
The dual nature of matter
imposes a limitation on the
simultaneous determination of
position and momentum of a
microscopic particle.

Based on this, Heisenberg

arrived at his uncertainty
principle.
Heisenberg uncertainty principle states that ‘It is
impossible to accurately determine both the position
and the momentum of a microscopic particle
simultaneously’.
The product of uncertainty (error) in the measurement is
expressed as follows.
Δx.Δp ≥ h/4π
where, Δx – uncertainty in determining the position and
Δp – uncertainty in determining the momentum,
respectively.
The uncertainty principle has negligible effect for
macroscopic objects and becomes significant only for
microscopic particles such as electrons.

Let us understand this by calculating the uncertainty

in the velocity of the electron in hydrogen atom.
(Bohr radius of 1st orbit is 0.529 Ǻ) Assuming that
the position of the electron in this orbit is determined
with the accuracy of 0.5 % of the radius.
Therefore, the uncertainty in the velocity of the electron is
comparable with the velocity of light. At this high level of
uncertainty it is very difficult to find out the exact velocity.
Schrodinger Equation:
• Objects exist in a specific
place at a specific time.
Classical
mechanics

• Objects exist in a haze of probability;

they have a certain chance of being at
Quantum point A, another chance of being at
point B and so on.
mechanics
Schrodinger Equation:
In classical mechanics, the physical state of the
particle is defined by its position and
momentum.
If we know both these properties, we can predict
the future state of the system based on the force
acting on it using classical mechanics.
However, according to Heisenberg’s
uncertainty principle both these properties
cannot be measured simultaneously with absolute
accuracy for a microscopic particle such as an
electron.
The classical mechanics does not consider the
dual nature of the matter which is significant for
microscopic particles.
As a consequence, it fails to explain the motion
of microscopic particles.
Based on the Heisenberg's principle and the dual
nature of the microscopic particles, a new
mechanics called quantum mechanics was
developed.
Erwin Schrödinger expressed the wave
nature of electron in terms of a
differential equation.
This equation determines the change of wave function in
space depending on the field of force in which the electron
moves.
The time independent Schrödinger equation can be
expressed as,

(1)
The above schrodinger wave equation does not
contain time as a variable and is referred to as
time independent Schrödinger wave equation.

This equation can be solved only for certain

values of E, the total energy. i.e. the energy of the
system is quantised.

The permitted total energy values are called

eigen values and corresponding wave functions
represent the atomic orbitals.
Main features of the quantum mechanical
model of atom :

1. The energy of electrons in atoms is quantised.

2. The existence of quantized electronic energy

levels is a direct result of the wave like properties
of electrons.
The solutions of Schrödinger wave equation gives
the allowed energy levels (orbits).
3. According to Heisenberg uncertainty principle, the
exact position and momentum of an electron can not
be determined with absolute accuracy. As a
consequence, quantum mechanics introduced the
concept of orbital.
Orbital is a three dimensional space in which the
probability of finding the electron is maximum.

4. The solution of Schrodinger wave equation for the

allowed energies of an atom gives the wave function
ψ, which represents an atomic orbital.
5. The wave nature of electron present in an
orbital can be well defined by the wave function
ψ.

6. The wave function ψ itself has no physical

meaning. However, the probability of finding the
electron in a small volume is known as
probability density and is always positive.
Quantum numbers:
The set of numbers used to describe the
position and energy of the electron in an atom
are called ‘quantum numbers.’

There are four quantum numbers,

i. Principal quantum number(n),
ii. Azimuthal quantum number(l),
iii. Magnetic quantum number(m) and
iv. Spin quantum number(s).
i. Principal quantum number(n):
Denoted by the symbol
‘n’.
Represents size and the
energy level in which the
electron revolves around
the nucleus.
n = 1,2,3,….
n = 1 represents K shell,
n = 2 represents L shell and
n = 3,4,5 represents M,N,O
shell respectively.
Maximum no. of. Electrons = 2n2
Shell Principal quantum Max. no. of. Electrons in a
number (n) shell(2n2)
K 1 2(1)2 = 2
L 2 2(2) 2 = 8
M 3 2(3) 2= 18
N 4 2(4) 2 = 32
ii. Azimuthal or subsidiary quantum number(l):

Represented by ‘l’.
l = 0 to (n-1), n = principal quantum number,
Each l value represents a subshell.
l 0 1 2 3 4
s p d f g
Max. no. of. Electrons = 2(2l+1)
Used to calculate the orbital angular momentum
using the formula,
Angular momentum = l(l+1) h/2π
Shell Principal Max. no. of. Azimuthal Max. no. of.
quantum Electrons in quantum Electrons
number (l) = 0
number (n) a shell(2n2) to (n-1)
2(2l+1)

K 1 2(1)2 = 2 0 2[2(0)+1] = 2

L 2 2(2) 2 = 8 0 2
1 2[2(1)+1] =6

M 3 2(3) 2= 18 0 2
1 6
2 2[2(2)+1] = 10
N 4 2(4) 2 = 32 0 2
1 6
2 10
3 2[2(3)+1] = 14
iii. Magnetic quantum number(ml):
Denoted by ml .
Values ranging from –l to +l through 0. i.e if l=1,
then m= -1,0,+1.
Represents the orientation of orbitals in space.
Zeeman effect – (splitting of spectral lines in a
magnetic field) provides the experimental
justification for this quantum number.
Magnitude of angular momentum – determined by
azimuthal quantum number,
Direction of angular momentum - given by
magnetic quantum number.
Shell Principal Max. no. of. Azimuthal Max. no. of. Magnetic quantum
quantum Electrons in a quantum Electrons number
number (n) shell(2n2) number (l) = 0 2(2l+1)
to (n-1)

K 1 2(1)2 =2 0 2[2(0)+1] = 2 0

L 2 2(2) 2 = 8 0 2 0

1 2[2(1)+1] =6 -1,0,+1

M 3 2(3) 2= 18 0 2 0

1 6 -1,0,+1

2 2[2(2)+1] = 10 -2, -1,0,+1,+2

N 4 2(4) 2 = 32 0 2 0

1 6 -1,0,+1

2 10 -2, -1,0,+1,+2

3 2[2(3)+1] = 14 -3, -2, -

1,0,+1,+2,+3
iv. Spin quantum number(ms):
Denoted by ‘ms’.
Represents the spin of the
electron.
Values are +1/2 and -1/2.
The electron in an atom not
only revolves around the
nucleus but also spins either in
clockwise direction(+1/2 ) or
anticlockwise direction(-1/2).
Spin is to be understood as
representing a property that
revealed itself in magnetic
fields.
Shapes of atomic orbitals:
The solution to Schrodinger equation gives the permitted
energy values called eigen values and the wave functions
corresponding to the eigen values are called atomic orbitals.
The square of the wave function |Ψ|2 is related to the
probability of finding the e-s within a given volume of space.
Let us analyse how |Ψ|2 varies with the distance from
nucleus (radial distribution of the probability) and the
direction from the nucleus (angular distribution of the
probability).
 Radial distribution function:
H atom n=1 and l=0. i.e. it occupies 1s orbital.

4πr2. R(r)2 –
radial
distribution
function.
r – radius.

The above plot shows that the maximum probability

occurs at distance of 0.52 Å from the nucleus. This is
equal to the Bohr radius.
It indicates that the maximum probability of finding
the electron around the nucleus is at this distance.
However, there is a probability to find the electron
at other distances also.
The radial distribution function of 2s, 3s, 3p and 3d
orbitals of the H – atom are represented as follows.
For 2s orbital, as the distance from nucleus (r)
increases, the probability density first increases,
reaches a small maximum followed by a sharp
decrease to zero and then increases to another
maximum, after that decreases to zero.
 The region where this
probability density
function reduces to
zero is called nodal
surface or a radial
node.
In general, it has been
found that ns-orbital
has (n–1) nodes.
In other words, number of radial nodes for 2s orbital
is one, for 3s orbital it is two and so on.
The plot for 3p and 3d orbitals shows similar pattern
but the number of radial nodes are equal to(n-l-1),
where n is principal quantum number and l is
azimuthal quantum number of the orbital.
 Angular distribution function:
The variation of the probability of locating the electron on a
sphere with nucleus at its centre depends on the azimuthal
quantum number of the orbital in which the electron is present.
For 1s orbital, l=0 and m=0.
The shape of the s orbital is spherical.
For p orbitals l=1 and the corresponding m values are -1, 0
and +1.
The three different m values indicates that there are three
different orientations possible for p orbitals. These orbitals
are designated as px, py and pz.
The shape of the p orbital is dumbbell.
px orbital – lobes present along the x-axis.
py orbital – lobes present along the y-axis.
pz orbital – lobes present along the z-axis.
For ‘d’ orbital l = 2 and the corresponding m values
are -2, -1, 0, +1,+2.
The shape of the d orbital is 'clover leaf '.
The five m values give rise to five d orbitals namely
dxy , dyz, dxz, dx2-y2 and dz2.
 2D - image

3D - image
For 'f ' orbital, l = 3 and the m values are -3, -2,-1,
0, +1, +2, +3 corresponding to seven f orbitals.
Seven f orbitals - fz3, fxz2, fyz2, fxyz, fz(x2−y2), fx(x2−3y2),
fy(3x2−y2).
Summary :

s orbital – Spherical,
p orbital – Dumbbell,
d orbital – Clover leaf and
f orbital – Tetrahedral.
Energies of orbitals
For one electron system like hydrogen, the energy of
the electron in the nth orbit is given by,

From this equation, we know that the energy

depends only on the value of principal quantum
number.
As the n value increases, the energy of the orbital
also increases.
The energies of various orbitals will be in the
following order:
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d
= 4f < 5s = 5p = 5d = 5f < 6s = 6p = 6d = 6f
< 7s.
The electron in the hydrogen atom occupies the 1s
orbital that has the lowest energy. This state is
called ground state.
When this electron gains some energy, it moves to
the higher energy orbitals such as 2s, 2p etc... These
states are called excited states.
However, the above order is not true for atoms
other than hydrogen (multi-electron systems).
(n+l) rule:
It states that, the lower the value of (n + l) for an
orbital, the lower is its energy. If two orbitals have
the same value of (n + l), the orbital with lower
value of n will have the lower energy.
Based on the (n+l) rule, the increasing order of
energies of orbitals is as follows:
1s < 2s < 2p < 3s < 3p < 4s <3d <4p <5s
<4d < 5p < 6s<4f< 5d < 6p < 7s < 5f < 6d.
Degeneracy:
3 different orientations of p orbital - px, py and pz.
Have same energies - degenerate orbitals.
However, in the presence of magnetic or electric
field, the degeneracy is lost.
In a multi-electron atom,
Electrostatic attractive force between the
electron and nucleus,
Repulsive force among the electrons.
Two forces are operating in the opposite
direction.
Results in the decrease in the nuclear force
of attraction on electron.
Net charge experienced by the electron is
called effective nuclear charge.
Effective nuclear charge depends on the
shape of the orbitals and it decreases with
increase in azimuthal quantum number l.
Order of the effective nuclear charge s > p
> d > f.
Greater the effective nuclear charge, greater
is the stability of the orbital.
Hence, within a given energy level, the
energy of the orbitals are in the following order.
s < p < d < f.
The energies of same
orbital decrease with increase
in atomic number.
For example, the energy of
the 2s orbital of H atom is
greater than that of 2s orbital
of Li and that of Li is greater
than that of Na and so on.
E2s(H) > E2s(Li) > E2s(Na)
> E2s(K).
 Aufbau principle:

Aufbau – in
German “Building
up”.
Orbitals are filled
with electrons in the
increasing order of
their energies.
e-s first occupy the lowest energy orbital.
Then e-s enter into the next higher energy
level and so on.
Aufbau principle is in accordance with (n+l)
rule.
 Pauli’s exclusion principle:

“No two electrons in an atom can

have the same set of values of all
four quantum numbers.”

Each electron must have unique

values for the four quantum
numbers(n, l, m and s.)
H atom:
n = 1, l = 0, m = 0 and s = +1/2.
He atom:
Two electrons
1st electron : n = 1, l = 0, m = 0 and s = +1/2
2nd electron : n = 1, l = 0, m = 0 and s = -1/2
 Hund’s rule of maximum multiplicity:
Aufbau principle does not deal with the filling of e -s in
degenerate orbitals(orbitals with same energy) like p x, py
and pz.

The answer is provided by Hund’s rule which states that,

“Electron pairing in the degenerate orbitals does not

take place until all the available orbitals contains one
electron each”.
Three p orbitals – 3 electrons 1st singly filled
in px, py and pz and after that only 4th electron
enters into px orbital and pairing occurs.
Similarly five d
orbitals – 6th electron
will start pairing,
Seven f orbitals – 8th
electron will start
pairing.
Example : Carbon (atomic no. 6) 1s2, 2s2, 2p2
 Electronic configuration

s orbital – max no. of. Electrons = 2

p orbital – max no. of. Electrons = 6
d orbital – max no. of. Electrons = 10
f orbital – max no. of. Electrons = 14
Few exceptions:
Example – Chromium(Cr) and Copper(Cu)
For chromium (Z=24)
Expected configuration : Reason:
1s2 2s2 2p6 3s2 3p6 3d4 4s2 Half filled and
Actual configuration : completely filled
1s2 2s2 2p6 3s2 3p6 3d5 4s1
configuration are
For copper (Z=29)
Expected configuration : more stable than
1s2 2s2 2p6 3s2 3p6 3d9 4s2 other configuration.
Actual configuration :
1s2 2s2 2p6 3s2 3p6 3d10 4s1
Stability of half filled and completely filled
orbitals:
Explained on the basis of
Symmetrical distribution of electrons and
Exchange energy.
i)Symmetrical distribution of electrons
Symmetry leads to stability.
Half filled and fully filled configurations have
symmetrical distribution of electrons.
Hence they are more stable than the unsymmetrical
configurations.
Degenerate orbitals have
equal energies.
Due to the symmetrical
distribution, the shielding of
one electron on the other is
relatively small.
Hence the electrons are more
strongly attracted by the
nucleus and it increases the
stability.
Exchange energy:
If two or more electrons with the same spin are
present in degenerate orbitals, there is a
possibility for exchanging their positions.

During exchange process the energy is

released and the released energy is
called exchange energy.

More number of exchanges - more

exchange energy is released.

More number of exchanges are

possible only in case of half filled and
fully filled configurations.
For example,
Chromium – [Ar]3d5
4s1.
The 3d orbital is half
filled and there are ten
possible exchanges.
Only six exchanges are
possible for [Ar]3d4 4s2
Hence, exchange energy for
the half filled configuration
is more.
This increases the stability of
half filled 3d orbitals.
The exchange energy is the
basis for Hund's rule.
 A N K Y O U
T H