(https://chemistryadda.com/home.

php)


ATOMIC STRUCTURE


2


What is an atom?

An atom is the smallest constituent unit of any matter that governs all chemical properties
of an element (remember all chemical, not physical).

Iron

1 atom

Attraction for magnet Yes Yes Yes Yes Yes

Copper

1 atom

Attraction for magnet No No No No No

The smallest unit is the atom of Fe which can give the all chemical property.

After this observation, we find out that it is an atom which gives that specific chemical
reaction of that compound. So that atom of each element is different. Now we became
interested that what are those things which make that atom unique. So we try to explore
the structure of the atom.

Atoms are so small (Fermi-meter, 1015 m ) that we can’t see inside an atom even by
electron microscope (magnification 107). It can only be observed but can’t be seen.

Discovery of sub atomic particles (1850):

(1) Discovery of cathode rays

(2) Discovery of anode (canal or channel rays)


Discovery of Cathode rays:

Experiment: When a gas with very low pressure is filled in a glass tube having two
electrodes (cathode and anode) at the high potential, we see a glow and image of the cross
at the anode side glass wall.

Observation:
(I) It signifies that there are some particles
which are attracted toward anode plate
i.e. having a negative charge.
(II) The rays were named as cathode rays
as these rays are emitted by the
cathode.
(III) Most important thing was that we got
same brightness and deflection at
anode side irrespective of the gas filled
in the tube, that means each gas have
that same type of particles.

Video: Click Here

Discovery of canal rays (or anode rays):

Experiment: Goldstein used a gas discharge tube which had a perforated cathode. When a
high electrical potential of several thousand volts is applied between the cathode and
anode, faint luminous "rays" are seen extending from the holes in the back of the cathode.

Observation:

(I) These rays are beams of particles

moving toward the anode so these
rays have positive charge.

(II) As these rays are coming from anode

so these are calle anode rays.

(III) Goldstein called these positive

rays "channel rays" or "canal rays"
because they were produced by the holes or channels in the cathode.

(IV) By the deflection in a magnetic field, revealed that the particles making up the ray were
not all the same mass. This gives the idea that gasses have positive charge particles.


Proposed Structure of atom:

(1) Thomson model of the atom

(2) Rutherford’s Alpha ray scattering experiment and Rutherford model for atom
(3) Bohr’s model of Hydrogen and Hydrogen like species
(4) Quantum mechanical model of atom (Schrödinger equation)

Thomson model of the atom:

Thomson model also called “Plum

pudding model” or watermelon model.
Thomson proposed a model of the atom
in which positive and negative charge
are embedded like watermelon seeds
are embedded in watermelon.

Specific feature – The mass of an atom

is uniformly distributed in the atom.

Video: Click Here

Rutherford experiment and Rutherford atomic model (1911):

Experiment: Rutherford does an experiment on thin gold foil (thickness approx. 100nm)
in which a stream of high velocity alpha particles was directed on gold foil.

Video: Click Here


The result of the experiment:

(1) Most of the alpha particles passed through the gold foil undeflected.
(2) A small fraction of alpha particles was deflected by a small angle.
(3) A very few alpha particles (approx. 1 in 20000) bounced back i.e. deflected by nearly
180°(not exactly 180°).
Observation of result:

(1) Most of the space in an atom is empty. As most of the alpha particles passed undeflected.
(2) A few positively charged alpha particles were deflected. The deflection must be due to
enormous repulsive force showing that the positive charge is not spread throughout
the atom as Thomson model has assumed. So positive charge is concentrated in a very
small space.
(3) Calculation by Rutherford shows that the volume occupied by nucleus is negligibly
small as compared to total volume of the atom. The radius of an atom is about 1010 m.
While that of the nucleus is 1015 m. We can realized it if the nucleus is cricket ball then
the atom is a sphere of radius about 5 km.

Rutherford atomic model:

(1) The positive charge and most of the mass of an atom is densely concentrated in the
extremely small region called nucleus.

(2) The nucleus is surrounded by electrons that move around with a very high speed in a
circular path called “orbits”, Similar to the solar system.


Maxwell electromagnetic theory:

Stationary charge Produced electric field

Charge with constant velocity Produced electric as well magnetic field
Charge with accelerated motion Produced electric as well as magnetic field & also
emits electromagnetic radiation

The drawback of Rutherford model:

According to Maxwell electromagnetic

theory, an electron revolving in an orbit
(accelerated charge particles) should emit
electromagnetic radiation.

So in rutherford model a revolving electron

will continuously emit energy so orbit will
thus continue to shrink and electron will
collapse into nucleus.

Calculation shows that it should take an

electron only 108 sec to collapse into the
nucleus. Thus the Rutherford model cannot explain the stability of the atom.


Dual nature of light: A light has a dual nature.

I. Wave Nature:

Reflection, refraction, diffraction, interference etc. are the properties of wave.

Young double slit experiment:

Video: Click here Click here

II. Particle nature:

Plank quantum theory:

Planck postulated that the energy of light is proportional to the frequency (‘  ’ Greek
symbol nu), and the constant that relates them is known as Planck's constant (h).
His work led to Albert Einstein determining that light exists in discrete quanta of energy,
known as photons.
hc
Ephoton = h or


Here h =plank constant ( 6.6  1034 joule  sec )


Continuous Discrete

Wave Particle

Photon Photon Photon Photon

Q. What is 1eV?

1 eV is defined as the energy gained by an electron when it has been accelerated by a

potential difference of 1 volt,

Energy of a photon (in eV):

hc (6.62  1034 J  sec)  (3  108 m / sec)

Ephoton  
 
(6.62  1034 J  sec)  (3  108  109 nm / sec)


(1.98 J  nm) 1 (1.98 eV  nm) 1240
  19
  eV
 1.6  10  (nm)


Photoelectric effect:

When light shines on metal, electrons can be ejected from the surface of the metal in a
phenomenon known as the photoelectric effect.

Collector plate

Video: Click here

Observation of photoelectric effect:

(I) For a given metal, there exists a certain minimum frequency (  ) of

incident radiation below which no photoelectrons are emitted. This frequency is
called the threshold frequency. Similarly there exists a certain maximum wavelength
(   ) of incident radiation above which no photoelectrons are emitted. This
wavelength is called the threshold wavelength.

(II) Increasing the frequency of the incident beam, keeping the number of incident
photons fixed increases the maximum kinetic energy of the photoelectrons emitted.

(III) Increasing the intensity of light would increase the current in galvanometer.

Intensity of light changes:

No of photoelectron per unit time changes, Current in galvanometer changes

Frequency of light changes:

KE of photelectron changes, Stopping potential changes

10


The result of photoelectric effect:
(I) A Photon has particle nature i.e. a packet of energy.
(II) The energy of each photon is determined by its frequency or wavelength.
(III) The energy of two or more photons is not additive in nature (i.e. absolutely particle
nature).This prove the particle nature of light.
(IV) Every metal has a certain work function (W or  ) .This shows the attraction of electron
from its parent atoms.

Intensity of light changes: Current in galvanometer changes

Frequency of light changes: Stopping potential changes

Derivation of photoelectric effect:

The total energy Ephoton of the incoming photon must be equal to the kinetic energy of the
ejected electron KEphotoelectron plus the energy required to eject the electron from the metal
surface i.e. W(or ) known as ‘work function’ of metal.

Ephoton  KEphotoelectron  W(or )

h KE  h

and

KE (in J)  h  h (or )

comparing with y  mx  c

If we want to compare in eV

h h
KE (in eV)     (or )
e e

11


Stopping potential:

5 eV KE 5 eV KE
e e

5V 5V

In photoelectric effect, if we apply a negative potential to the collector plate ‘C’ with respect
to the metal plate P and gradually increase it, the photoelectric current becomes zero at a
certain negative potential. The negative potential on the collector at which the
photoelectric current becomes zero is called the stopping potential or cut off potential.

Stopping potential (in V)  KE (in eV)

Final result of particle nature: Electromagnetic energy is quantized. It can be produced,

lost ,transfer etc. only in quantised form.

12


Bohr’s model for Hydrogen and hydrogen-like atom:

With the support of plank’s theory (i.e. energy is quantized), Bohr explains the hydrogen
atom. He proposed the following postulates.

(I) Electron in the hydrogen atom move around the nucleus in a circular path of fixed
radius as well as energy. These paths are called orbits, stationary orbits or allowed
energy state.

(II) The energy of an electron in the orbit does not change with time. [As energy is
quantized, so a revolving electron can’t loss energy in a continuous manner as it was
thought in Rutherford’s atomic model](Agar energy quantized hai to wah slowly
slowly kaise lost ho sakti hai)

(III) The electron will move from a lower stationary orbit to higher stationary orbit for
this it takes a specific amount of energy. When this electron return to its previous
orbit it releases this energy in the form of a photon (or electromagnetic radiation).

E2  E1
(IV) The frequency  of radiation absorbed or emitted is given by  
h

(V) The angular momentum of an electron in an nth orbit is given by

h
me vr  n. ;n  1,2,3..........
2

Bohr has no explanation for this but later it was found out that Bohr was absolutely
correct.

Derivation of Bohr’s model for Hydrogen and Hydrogen-like atoms:

Pre Required Formulas:

mv2
Fcentrifugal  v
r
r m

1 Q1  Q2 +Q1 r +Q2
Fculombic  .
4 r2
1 Q1  Q2
P.E   .
4 r

13


Fcentrifugal  Fculombic
mv2 1 (Ze).e
 .
r 4 r2
or
1
mv2r  .Ze2 ......(I)
4
From postulate (V)
h
mvr  n. .......(II)
2

now (I)  (II)

1 2 e2  Z 
v .Ze2   .....(III)
4 n.h 2hε °  n 
Z
v  2.19  108 cm / sec
n

put the value of 'v' in (II)

h nh2   n 
r  n. 
2 m  v 2m  e2  Z 
h2ε °  n2 
   ........(IV)
mπe2  Z 

n2 
r  0.53 A
Z

1
K.E.  mv2
2
 1  e2 Z 2  e 4 m  Z2 
  m       ....(V)
 2  2 n   8ε °2h2  n2 
 

1 Ze  e
P.E  
4 r
after putt ing the value of r
e4m  Z2 
P.E    
42h2  n2 

14


 e4m  Z2  e4m  Z2 
Total energy E      
42h2  n2  82h2  n2 
e4m  Z2 
    K.E.
82h2  n2 
 Z2 
E  13.6  2  eV
n 

Time Period of e in orbit  Total time taken to complete one revolution

distance 2r
 
velocity v

For Hydrogen atom:

n=3 E=-1.51 eV Second excited state

or Third Bohr orbit
n=2 E=-3.4 eV First excited state
or Second Bohr orbit

n=1 E=-13.6 eV Ground state or First Bohr orbit

or Bohr orbit

15


Hydrogen line spectra:

Experiment: Hydrogen gas is filled at low pressure in a gas discharge tube. The atom of
hydrogen gas will acquire energy from the electric field and electron in the atoms jump to
high energy orbit, after a very short time they return back to their original orbit, as well as
release the acquired energy in the form of electromagnetic radiation. This radiation is
passed through a slit and after that it is allowed to pass through a prism. The prism breaks
the radiation according to their frequency. Then we get thin line strips on screen, these
lines are known as line spectra of the hydrogen atom. Spectral emission occurs when
electron transitions, or jumps, from a higher energy state n2 to a lower energy state n1 .

A transition from higher energy state n2 to a lower energy state n1 is shown as:

n2 
 n1

Video: Click here

Derivation for line spectra:

e4m  Z2 
E Z,n    
82h2  n2 

e4m  Z2  e4m  Z2 
E Z,n1     E Z,n2    
82h2  n12  82h2  n22 

16


 e4m  Z2 Z2   1 1 
E Z,n2 EZ,n1  2 2
 2   13.6Z2  2  2  eV
 2
8 h  n1 n2  n n 
 1 2
by equating this energy with the energy of photon
hc e4m  Z2 Z2 
   
 82h2  n12 n22 

1 e4m  Z2 Z2 
   
 82h3c  n12 n22 

1  1 1 
 R  Z2  2  2 
 n n 
 1 2

R= Rydberg’s constant (1.097×107/m)

Series n1 n2 Spectral region

Lyman [1915] 1 2, 3, 4…. Ultra violet
Balmer [1885] 2 3, 4, 5, 6 Visible
7, 8, 9 ... Ultra violet
Paschan [1896] 3 4, 5, 6… Infrared
Brackett [1922] 4 5, 6, 7… Infrared
P-fund [1925] 5 6, 7, 8… Infrared

All names of series are known after their discoverers.

Also:

n=2 
 n=1 L First line of Lyman
n=3 
 n=1 L Second line of Lyman
n=4 
 n=1 L Third line of Lyman

n=3 
 n=2 B First line of Balmer
n=4 
 n=2 B Second line of Balmer

Maximum number of spectral lines:

(I) From any higher energy level ‘n’ upto finally ground state
n(n  1)
=
2
(II) From any higher energy level ‘ n2 ’ upto finally n1
n(  n 1) (n2  n1 )(n2  n1  1)
= = ; n  n2  n1
2 2

17


Toward quantum-mechanical model of the atom

(I) Dual behavior of the matter:

Initially, it was found out that only light has dual nature (wave as well as particle) but in
1924 de-Broglie says that matter also exhibits dual behavior. This means that as a photon
has momentum (particle nature) as well as the wavelength (wave nature), a moving
microscopic particle also have momentum as well wavelength.

Experiment:

As double slit experiment use light for wave interference. Another experiment for double
slit but using electron beam was done and we find out this showing the same result as with
light. This experiment proves the de-Broglie statement.

A similar experiment was demonstrated with proton, neutron and various atoms. In 1994,
it was demonstrated with iodine molecule I2, which is nearly 50000 times more massive
than an electron. In 1999 it was demonstrated with fullerenes C60 and C70.

Apparently, microscopic objects as electrons, protons, atoms and molecules travel as

matter wave rather than only matter.

According to de-Broglie every object in motion has a wave character. The wavelength
associated with the ordinary object is so short (because of their heavier mass) that their
wave properties cannot be detected.

18


De-Broglie wavelength:

De-Broglie gives following relation between wavelength λ and momentum ‘p’ for a particle
having mass ‘m’ and velocity ‘v’.

h h
  : h = plank constant
p mv

Derivation: By Einstein relation

E  mc2
hc
 mc2

h h
 , or  matter 
mc mv

(I) If mass and Kinetic energy of particle is given:

1
KE  mv2
2
2KE
v
m
h h
 
2KE 2 m KE
m
m
h

2 m KE

(II) If a particle having charge ‘q’ , mass ‘m’ is accelerated by a potential V:

K.E  q.V

h 1.226
 ;for electron   nm
2m qV V

Particle Charge mass

electron -e mp / 1824
proton +e mp
neutron 0 mp
Alpha particle +2e 4 mp
Li3 +3e 7 mp

19


Number of de-Broglie wave in Bohr orbit:

In Bohr model, an electron wave moving in a circular orbit of radius around the nucleus
always remain continuously in phase, so the circumference of orbit must be an integral
multiple of the wavelength.

By Bohr orbital angular momentum:

h
mvr  n.
2
h
2r  n
me v
2r n 
Circumference of n th orbit  n  

n2 
r  0.53 A
Z

i.e. r  n2

9r

4r

+ r

n=1

n=2

n=3

20


Drawback of Bohr’s model:

1. Bohr treated electrons as particles where according to de Broglie's hypothesis, having a

very low mass, electron also exhibits wave nature.

2. Bohr's model was adequate only for species having only one electron e.g. Hydrogen, He+,
Li+2 etc. Bohr's model could not explain the spectra of multi-electronic atoms.

3. Bohr's model was two-dimensional where as an atom is three-dimensional.

4. Using a better spectrometer, the spectra showed very fine lines. Bohr's model could not
explain the origin of those fine lines. (Solved by Arthur Sommerfield who imagined
electrons orbiting in different planes and having elliptical orbits.)

5. Bohr's model could not explain the effect electric field and magnetic field on spectra.
(Stark effect and Zeeman effect)

The Zeeman effect is the effect of splitting a spectral line into several components in the
presence of a static magnetic field. It is analogous to the Stark effect, the splitting of a
spectral line into several components in the presence of an electric field

6. In Bohr's equation, the momentum and position of electron, revolving around the nucleus
were well defined. But, according, Heisenberg's Uncertainty principle, it is impossible to
measure the position and momentum of electrons precisely. If the position is measure
with maximum precision, there will be uncertainty in the value of momentum and vice
versa.

21


Heisenberg’s uncertainty principle:

If a particle is very small in size and very fast in speed then this particle has significant
wave nature. The uncertainty principle actually states a fundamental property of quantum
systems (matter wave), and is not a statement about the observational success of current
technology.

Just like as the speed of any particle cannot be greater than the speed of light.

Video: Click here & Click here

Wave
Completely unlocalised

Matter
Completely localised

Heisenberg principle is just like seeing darkness and light simultaneously. Now consider a
fast moving matter, it becomes matter wave, it has two things one is wave (completely
unlocalised) and other is matter (completely localised). Heisenberg says that we cannot
know both things simultaneously without any error.

Heisenberg’s uncertainty principle state that “it is impossible to know the exact position
and velocity (momentum or de Broglie wavelength) simultaneously of a quantum particle”

There will be a certain error in position (∆x) and velocity (∆v) and both are related as

h
x   v 
4m
or
h p  mv
x   p 
4
h
E   t 
4

22


Consider the following mathematical representation of localisation of multiple
wave (multiple wave i.e. multiple velocities), to localise the wave at one point i.e.
localisation a matter at one point.

More localisation (i.e. x is small), more need of waves

(i.e.  is large, i.e. v is large ).

23


Quantum mechanical model of the atom:

Bohr model: like water in bucket

Quantum model: like water in cloud

As we move from macroscopic particles to microscopic particles, the wave nature of

particles become significant. So there was an absolute necessity to explain the atomic
model by considering the wave nature. The branch of mechanics that deals with the
mathematical description of the motion and interaction of subatomic particles,
incorporating the concepts of quantization of energy, wave–particle duality, the
uncertainty principle, etc is known as quantum mechanics.

Schrödinger equation: Schrödinger uses the principle of quantum mechanics and gives
an equation for an atom that correlated the wave property of the electron with energy.

We can understand this equation by taking any example that has constant energy with time
(as the atoms have)

Some examples are:

(I) Standing wave in a string

(II) Pendulum with simple harmonic motion

(III) L-C oscillation

Explanation by using standing wave in a string:

The equation of standing wave can be given as

sin2 x ………. (I)

  A.


Ψ=Amplitude of displacement at distance ‘x’

A=Max. the amplitude of standing wave

λ= Wavelength of wave

Differentiate the eq. (I) with respect to x

d 2 2x
 A cos
dx  
d2  42 2x 42
  A sin    .....(II)
dx2   2

Now total energy of the system can be given as:

24


Etotal  KE  PE
1
Etotal  mv 2  V
2
2(E V)
so, v 2 
m

By de-Broglie relation:
h2
2 
m2 v 2
h2
2 
2m(E V)
After putting the value of  2 in Eqn. (II)
d2  42 .2m(E V)
2
 .
dx h2
or
d2 82m(E V)
 .  0 ....(III)
dx 2 h2
Eqn. (III) is a Schrödinger wave eq. in one-dimensional (only in x-axis). For electron
moving in three dimensions, it can be modified as

2 2  2 82m(E V)

   .  0 ....(IV)
x2 y 2 z2 h2

Ψ- Wave function is a function of electron’s coordinates and in fact can be expressed as

functions of each coordinated

Ψ(x, y, z)= X(x)Y(y)Z(z)

But usually, it is done in spherical polar

coordinates.
X=r. sinθ.cos∅
Y=r. sinθ.sin∅
Z=r. cosθ
So the wave function becomes as

Ψ(r, θ, ∅) = R(r).Ɵ(θ).∅(∅)

= R  r  .Ylm (, ) : R=Radial function

Ylm (  , ) =Spherical harmonic of degree l and order m

Spherical harmonics are special functions defined on the surface of a sphere. (Similar to
circular function generate sine and cosine function) The actual value of Ψ can be
expressed as:

25


 3 l
r
 2  (n l 1)!  na0  2r   2l 1  2r   m
 n,l,m (r, , )    .e    Ln l 1    .Yl (, )
 na0  2n[(n  l)!]  na0    na0  

  h2
Here a0  is Bohr radius.
me2

L2nll11 =generalised Laguerre polynomial of degree n-l-1

n, l, ml are the principle, azimuthal and magnetic quantum number respectively , which
takes the value
n=1, 2, 3.....
l=0, 1, 2...... (n-1)
ml =-l......0......+l
L2nll11 is laguerre polynomials. First four values of this can be given as:

L0 (r)  1
L1 (r)  r    1
r2 (  2)(  1)
L2(r)   (  2)r 
2 2
 r3 (  3)r2 (  2)(  3)r (  1)(  2)(  3)
L3(r)     
6 2 2 6

n, l, ml are the Principal, Azimuthal and Magnetic quantum number which are defined as
follows.

26


 Ψ = The wave function  n,l,ml is a mathematical function whose value depends upon
spherical polar coordinates (r, ,  ) of the electron and characterize by the quantum
numbers n, l and ml
Ψ2 = Ψ2 in quantum mechanics interpreted as the probability of finding an electron at any
point.

(1) Principal quantum number (n)

(I) It was proposed by Bohr and denoted by ‘n’

(ii) It determine the average distance between electrons and nucleus, means it denote the
size of atom
(III) It determines the energy of an electron in an orbit where the electron is present.
(IV) The maximum number of electron in an orbit represented by this quantum number
is 2n2.
(V) The value of energy increases with the increasing value of n
(VI) It represents the major shell from which the electron belongs.

(2) Azimuthal quantum number or angular quantum number (l)

(I) It determines the number of subshell or sublevel to which the electron belongs.
(II) It tells about the shape of the subshell.
(III) l can have any value from 0,1,2..........to (n–1)
(IV) The number of electron in a subshell is given by 2(2l+1)

(3) Magnetic quantum number ( ml )

(I)It gives the number of permitted orientation of subshell i.e. orbitals
(II)The value of ml varies from –l to +l through zero.
(III)It tells the splitting of spectral lines in the magnetic field.
(IV)For a given value of ‘n’, the total value of m is equal to n2
(V)Degenerate orbitals: orbitals having the same energy is known as degenerate orbitals.

(4) Spin quantum number( ms or s)

1 1
(I) The value of ‘s’ is  and  which signifies the spin of an electron on its axis during
2 2
the movement.
Note: spin quantum number is not the result of Schrodinger equation.

27


Atomic orbital:
“An atomic orbital is a mathematical function that describes the wave-like behaviour of an
electron around the nucleus” This function gives the probability of finding of electron
around the atom’s nucleus.

The wave pattern is produced when the free end is

vibrating with at just the right frequency.
The pattern formed called standing wave pattern.
Now, what would you call this. We can’t predict that
where the rope will be at any time. We only can say that
the probability of a finding of rope in the region is
100%.We can say it rope orbital, this orbital can be
represented by a mathematical equation of standing
wave.
[Now suppose that vibrating system is also rotating
then we got 2D to 3D formation]

Shape of orbitals:
‘s’ type orbitals (l=0)
z
z

x y
x y

2s 3s
‘p’ type orbitals (l=1)
z z z

x y x y x y

2px 2py 2p z
28


‘d’ type orbitals (l=2)
z z

y x
x y

3d xy 3d yz 3d zx

x y x y

3d x-y
2 2 3dz2

29


Nodes: In an orbital, nodes are defined as the points where the probability of finding an
electron becomes zero. Two types of nodes are defined in orbitals.

(I) Radial nodes or spherical node: Radial nodes are defined in terms of radial distance
(r) from the nucleus. The total number of radial nodes for any orbital is given as n–l–1.

Radial nodes= n–l–1

(II) Angular nodes: Angular nodes are defined in terms of angle θ and the ∅. The number
of angular nodes in any orbital is given as the value of l.

Angular nodes=l

Total nodes=Angular nodes+Radial nodes=n–1

Nodal plane: Nodal plane is the plane at which the probability of finding of electron is zero.

# ‘s’ orbital has no nodal plane,

# ‘p’ orbital has one nodal plane
# ‘d’ orbital (except dZ2 ,it has two conical surface) has two nodal plane.

30


Orbital and analysis of nodes and nodal plane:

(I) s orbital:
#. Radial Node: 1s have zero radial node, 2s have 1 radial node
#. Angular Node: ‘s’ orbitals does not have angular node
#. Nodal Plane: ‘s’ orbitals does not have any nodal plane
#. 2 for ‘s’ orbitals depends only on radial distance ‘r’

(II) p orbital:
#. Radial Node: 2p have zero radial node, 3p have 1 radial node
#. Angular Node: ‘p’ orbitals have 1 angular node
#. Nodal Plane: ‘p’ orbitals have one nodal plane
#. 2 for ‘p’ orbitals depends on radial distance ‘r’,  and 

31


(III) d orbital:
#. Radial Node: 3d have zero radial node, 4d have 1 radial node
#. Angular Node: ‘d’ orbitals have 2 angular node
#. Nodal Plane: ‘d’ orbitals have 2 nodal plane ( dZ2 does not have nodal plane)

#. 2 for ‘d’ orbitals depends on radial distance ‘r’,  and 

32


Radial probability distribution curves:
Three types of plots are plotted

(I) Radial wave function (Ψ) and radial distance(r):

r
1s

0 0.2 0.4 0.6

(r)nm

r
2s radial node

0.4
0 0.2 0.6
(r)nm

2p

Imp points: The value of  is maximum near the nucleus for all ‘s’ orbitals. While The value of 
is minimum at nucleus for all ‘p’ and ‘d’ orbitals

33


(II) Radial wave function (Ψ2) and radial distance(r):

Radial probability = 2

[Example for 2s: Suppose you are travelling from city ‘A’ to city ‘C’ via city ‘B’. Just as you
leave city ‘A’ there is very strong rain. The intensity of rain decreases as we go far from city
‘A’. As you reach city ‘B’ the rain stops, but as we leave city ‘B’ it again start raininig as well
as increasing and becoming high in midway to city ‘C’. After then it again start decreasing
and up to city ‘C’ and it becomes very low (cheenta-chaanti)]. Draw the 2D plot rain
intensity v/s travelling from city ‘A’ to city ‘C’.
A 
 B 
C

 r
1s

0 0.2 0.4 0.6

(r)nm

 r
2s radial node

0 0.2 0.4 0.6

(r)nm

2p

34


 πr2Ψ2) and radial distance(r):
(II) Radial wave function (4π

4  4 
Volume of shell=  (r  dr)3    r3 
3  3 
= 4r2dr ; assuming dr3 and dr2 as zero

Radial shell probability = 4r2dr2

Radial shell probability distribution = 4r22

1s

2s

2p

Imp points: The value of 4r2 2 is zero at nucleus for all ‘s’ ‘p’ and ‘d’ orbitals, and local maxima
will always appear before the maxima.

35


Filling of orbitals in atom (Making of an atom from scratch)

Electronic configuration: The distribution of electrons in various orbitals is known as electronic

configuration. The model of the atom is built in such a way that an electron occupies its
most stable position available. [Similar to as a bus conductor arrange passenger according
to its best suitable way].This produced an atom in its lowest energy (most stable) state
[Conductor arrange passenger in a most economical way].

The filling of an electron in the ground state is determined by the following rules.

(1) Aufbau principle):

Aufbau is a german word having meaning ‘building up’. This principle states that in the
ground state of the atom, the orbital with a lower energy is filled up first before the filling
for the orbital with a higher energy.
Energy of orbital is given as ‘n+l’
If (n+l) is same then lower the value of n, lower the energy of orbital.
Ex: 3d, 4p, 5s all have n+l=5,
But the energy of orbital is in the order of
3d < 4p < 5s

(2) Hund’s rule of maximum multiplicity:

This rule states that electron pairing in orbital of similar energy i.e. degenerate orbitals (ex
px ,py ,pz or dxy ,dyz ,dzx ,d x2 y2 ,dz2 ) will not take place unless all such orbitals contain one
electron each with parallel spin states.

36


(3) Pauli’s Exclusion Principle: The principle states that no two electrons in one atom can have
four quantum number the same.

Exchange energy: The extra stabilization in the orbitals arises whenever two or more electrons
with the same spin are present. These electrons tend to exchange their positions and
energy released due to this exchange is called exchange energy.

Stability of half and full filled orbital: More the exchange energy, more stable the configuration.
So if a subshell is half filled or fully filled it is more stable than the partially filled subshell
that’s why

24 Cr is more stable than

24 Cr
similarly

29 Cu is more stable than

29 Cu

Some other formulas:

h
(I) Orbital angular momentum= l(l 1).  l(l 1).
2
h
(Here ħ= , known as Dirac function)
2

h
(II) Spin angular momentum: S(S 1).
2
n
S= , and ‘n’ is the number of unpaired electrons
2
(III) Spin magnetic moment:   n(n  2)BM
n= number of unpaired electrons
1 BM= 9.27  1024 J/Tesla

37


 () () () () ()

Contact Us: [email protected] (mailto:[email protected])