MODULE-I

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INTRODUCTION TO ATOMIC STRUCTURE

General Chemistry
CHY-111
1

By: Dr. Lalit Prasad

 CONTENTS

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Structure of the Atom,
Introduction to Periodic Table,
Evolution of Atomic Theory,
Thomson’s plum pudding model, Rutherford’s and, Bohr’s models,

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Rutherford-Geiger-Marsden Experiment,
Planck-Einstein Relationship, Black body radiation, Planck’s constant;
Bohr’s postulates;
Matter-Energy interactions involving hydrogen atom;
quantum states; electron orbital transitions; s, p, d, f, orbital's;
electronic configuration based on quantum states;
Bohr-Sommerfield Model, Quantum numbers;
Balmer and Pfund Series, Rydberg Equation;
Stern-Gerlach Experiment;
Aufbau Principle; Pauli’s Exclusion Principle; Hund’s Rule;
Heisenberg’s Uncertainty Principle; Wave- Particle duality;
Schrodinger Equation; Simple Harmonic Oscillator; Particle in a Box. 2
 Structure of atom
 John Dalton (1805) considered that all matter was composed of small
particles called atoms.

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He visualised the atom as a hard solid individual particle incapable of
subdivision.
At the end of the nineteenth century there accumulated enough
experimental evidence to show that the atom is made of still smaller

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particles.
These subatomic particles are called the fundamental particles. The
number of subatomic particles now known is very large. For us, the three
most important are the proton, neutron and electron.
How these fundamental particles go to make the internal structure of
the atom, is a fascinating story.
The main landmarks in the evolution of atomic structure are :
1896 J.J. Thomson’s discovery of the electron
1909 Rutherford’s Nuclear Atom
1913 Mosley’s determination of Atomic Number
1913 Bohr Atom
1921 Bohr-Bury Scheme of Electronic Arrangement 3
1932 Chadwick’s discovery of the neutron.
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 Structure of atom

In 1886, E. Goldstein discovered new radiations in gas discharge and called them canal
rays. These rays were positively charged. This later led to the discovery of the positively
charged particles called protons in the atom. In 1896, J.J. Thomson discovered the
presence of the negatively charged particles
called ELECTRONS in the atom.
In 1917, Ernest Rutherford discovered positively charged particle called Proton.

In 1932 Chadwick discovered the presence of particles having no charge in the atom
called neutrons

Subatomic Unit Unit Charge in Mass in

Symbol mass
particles charge Coulomb amu
1
1H
-1 +1.60 × 10-19 1.007825
Proton 1

1
0n 0
Neutron 1.008665
1 0

5
0
1 e
Electron -1 1.60 × 1019 5.489×10-4
Negligible
 INTRODUCTION TO PERIODIC TABLE

THE PERIODIC LAW

Mendeleev understood the ‘Periodic Law’ which states:

 When arranged by increasing atomic number, the chemical elements display

a regular and repeating pattern of chemical and physical properties.

 Atoms with similar properties appear in groups or families

(vertical columns) on the periodic table.

 They are similar because they all have the same number of valence
(outer shell) electrons, which governs their chemical behavior.
A DIFFERENT TYPE OF GROUPING
 Besides the 4 blocks of the table, there is another
way of classifying element:
 Metals

 Nonmetals

 Metalloids or Semi-metals.

 The following slide shows where each group is

found.
 METALS, NONMETALS, METALLOIDS

 There is a zig-zag or
staircase line that
divides the table.

 Metals are on the left

of the line, in blue.

 Nonmetals are on the

right of the line, in
orange.
 Noble Gas
Halogen
Group
Period
% Alkali Earth Metal
Alkali Metal
PERIODIC PROPERTIES
 Dalton’s Atomic Theory

Elements are made of extremely small particles

called atoms.

Atoms of a given element are identical in size,

mass, and other properties; atoms of different

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elements differ in size, mass, and other
properties.

Atoms cannot be subdivided, created, or

destroyed.

Atoms of different elements combine in simple

whole-number ratios to form chemical
compounds.

In chemical reactions, atoms are combined,

separated, or rearranged. 11

Dalton’s theory forms the foundation of Modern Theoretical Chemistry

 Thomson model of an atom
 According to Thomson an atom is similar to a Christmas
pudding. The pudding had positive charge and the electrons

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having negative charge were like plums on the pudding.
 He proposed that :-
i) An atom consists of a positively charged sphere and the
electrons are embedded in it.
ii) The negative and positive charges are equal in magnitude
So the atom as a whole is electrically neutral

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 Thomson’s Experiment

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- +
Voltage source

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 Passing an electric current makes a beam appear to move from the
negative to the positive end
13

KS 13
 Thomson’s Experiment

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Voltage source

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-
 By adding an electric field he found that the moving pieces were
negative
14

KS 14
 Problems with Thomson’s Model

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How does the atom emit radiation?

This model soon came into conflict with experiments by Rutherford

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Rutherford-Geiger-Marsden gold foil experiment in 1909 disproved the
Plum Pudding Model and showed that instead of a soup of positive
charge, an atom consisted of a small nucleus of strong positive charge
paving the way to Rutherford’s Atomic Model.

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 RUTHERFORD’S MODEL
Atom consist of two parts:

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(a) Nucleus: Almost the whole mass of the atom is concentrated in this small
region

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(b)Extra nuclear part: this is the space around the nucleus in which electrons are
revolving at high speeds in fixed path

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Rutherford-Geiger-Marsden Experiment

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 Rutherford model of atoms
Rutherford’s alpha scattering experiment :-

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Rutherford allowed a beam of fast moving alpha particles ( α –particles)
having positive charge to fall on a thin gold foil. He observed that :-

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i) Most of the α – particles passed straight through the gold foil.
ii) Some of the α – particles were slightly deflected by small angles.
iii) Very few α – particles appeared to rebound.

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Based on these observations, Rutherford proposed a model of the

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atom which is named after him. This is also called the Nuclear
Atom. According to it :

Atom has a tiny dense central core or the nucleus which

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contains practically the entire mass of the atom, leaving
the rest of the atom almost empty. The diameter of the
nucleus is about 10-13 cm as compared to that of the atom 10–8 cm.

The entire positive charge of the atom is located on the

nucleus, while electrons were distributed in vacant space
around it.

The electrons were moving in orbits or closed circular

paths around the nucleus like planets around the sun.
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 Defects of Rutherford’s model of the atom

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 Any particle in a circular orbit would undergo acceleration and during
acceleration the charged particle would radiate energy. So the revolving
electrons would lose energy and fall into the nucleus and the atom would be

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unstable. We know that atoms are stable.
Rutherford’s model of an atom

Negatively charged
electron
- -
Negatively charged
electrons in orbits
around the nucleus

+
-
Very small positively Positively charged
charged nucleus nucleus20
DEFINITION OF A BLACK BODY

A black body is an ideal body which

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allows the whole of the incident radiation
to pass into itself (without reflecting the
energy) and absorbs within itself this
whole incident radiation (without passing

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on the energy).

This propety is valid for radiation

corresponding to all wavelengths and to
all angels of incidence. Therefore, the
black body is an ideal absorber of incident
radaition.

A body's behavior with regard to thermal

radiation is characterized by its
transmission τ, absorption α, and 21
reflection ρ. For a black body, τ=0, α=1,
and ρ=0.
 BLACKBODY RADIATION

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Blackbody radiation—radiation emitted by a body that
emits (or absorbs) equally well at all wavelengths
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 Basic Laws of Radiation
Stefan Boltzmann law
All objects emit radiant energy.

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Hotter objects emit more energy than colder objects. The amount of energy
radiated is proportional to the temperature of the object raised to the fourth
power.

 This is the Stefan Boltzmann Law

F =  T4
( F= energy flux is the rate of transfer of energy through surface)

F = flux of energy (W/m2) (W/m2 :Watts per sq. meter)

T = temperature (K)
 = 5.67 x 10-8 W/m2K4 (a constant)
The hotter the object, the shorter the wavelength () of emitted energy. 23

max = hc/5kT
This is Wien’s Law
BLACK-BODY RADIATION LAWS
2ckT
The Rayleigh-Jeans Law I ( , T ) 
4
It agrees with
experimental
measurements for long

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wave-lengths.
It predicts an energy
output that diverges
towards infinity as
wavelengths grow
smaller.
The failure has become
known as the ultraviolet
catastrophe. 24

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 Planck’s Law of Black Body Radiation

The Planck’s Law of Black Body Radiation states in

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terms of wavelength:
2hc 2 1
I ( , T ) 
5 hc

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e kT  1

• The above equation related intensity of

emission with Temperature and
wavelength.
• It fits well with experimental observation
of black body radiation.

• As opposed to classical model of

continuous energy distribution, energy is
emitted in forms of quantized packets,
where h is Planck’s constant: 25

E  h  hc / 
Hotter objects emit at
shorter wavelengths.

max = 3000/T
Sun
Earth

1000 100 10 1 0.1 0.01

Hotter objects emit more

 (m) energy than colder objects

F =  T4
 Applications of Black Body Radiation

• Roughly we can say that the stars radiate like blackbody

radiators. This is important because it means that we can
use the theory for blackbody radiators to infer things about
stars like its effective temperature.

• Interesting applications include designing camouflage

and radar absorbent materials.
 Planck-Einstein Relationship

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The wave theory of transmission of radiant energy appeared to imply
that energy was emitted (or absorbed) in continuous waves.
In 1900 Max Planck studied the spectral lines obtained from hot-body
radiations at different temperatures.
 According to him, light radiation was produced discontinuously by the

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molecules of the hot body, each of which was vibrating with a specific
frequency which increased with temperature.
 Thus Planck proposed a new theory that a hot body radiates energy not
in continuous waves but in small units of waves.
The ‘unit wave’ or ‘pulse of energy’ is called Quantum (plural, quanta).
In 1905 Albert Einstein showed that light radiations emitted by
‘excited’ atoms or molecules were also transmitted as particles or quanta of
energy. These light quanta are called photons.

The general Quantum Theory of Electromagnetic Radiation in its

present form may be stated
as :
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(1) When atoms or molecules absorb or emit radiant energy, they do so
in separate ‘units of waves’ called quanta or photons. Thus light
radiations obtained from energised or ‘excited atoms’ consist of a stream

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of photons and not continuous waves.
(2) The energy, E, of a quantum or photon is given by the relation
E = hν; where ν is the frequency of the emitted radiation, and h the Planck’s
Constant= = 6.626 x 10 -34 joule seconds (J s)

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We know that c, the velocity of radiation, is given by the equation
c = λν
Substituting the value of ν from E =hc/λ
(3) An atom or molecule can emit (or absorb) either one quantum of
energy (hν) or any
whole number multiple of this unit.
Thus radiant energy can be emitted as hν, 2hν, 3hν, and so on, but never as 1.5
hν, 3.27 hν,
5.9 hν, or any other fractional value of hν i.e. nhν
Quantum theory provided admirably a basis for explaining the photoelectric
effect, atomic
spectra and also helped in understanding the modern concepts of atomic and
molecular structure. 29
 Planck-Einstein Relationship

E  h  hc / 

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h = Planck’s Constant = 6.626 x 10 -34 joule
seconds (J s)

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Energy could be gained or lost in individual units or
packets, with energies that are whole number
multiples of the constant, h.

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 PLANCK’S QUANTUM THEORY

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Radiant energy is emitted or absorbed discontinuously in
the form of quanta.

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c
E  h  h  hc

  Wavelength
  Frequency
  Wave number
h  Plank ' s cons tan t
 6.626  1034 Js

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ILLUSTRATIVE PROBLEM
The ratio of the energy of a photon of 2000 Å wavelength
radiation to that of 6000 Å wavelength radiation is

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(a) ¼ (b) 4
(b) ½ (d) 3

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Solution:

hc hc hc
E  h  E1  E2 
 1 2
0
E1  2 6000 A
   3
E2 1
0
2000 A
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Hence, answer is (d).
 Bohr’s model of an atom
In 1913 Niels Bohr proposed a new model of atom which explained some of these
things and also the emission spectrum of hydrogen.

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Bohr’s theory was based on Planck’s quantum theoryand was built on the following
postulates.
i) An atom has a positively charged nucleus at its centre and most of the mass of the
atom is in the nucleus.

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ii) The electrons revolve around the nucleus in special orbits called discrete orbits.
iii) These orbits are called shells or energy levels and are represented by the letters
K, L, M, N etc. or numbered as 1, 2, 3, 4, etc.
iv) While revolving in the discrete orbits the electrons do not radiate energy.
v) An electron can move from one energy level to another by quantum or
photon jumps only.
When an electron resides in the orbit which is lowest in energy
(which is also closest to the nucleus), the electron is said to be in the
ground state.
When an electron is supplied energy, it absorbs one quantum or
photon of energy and jumps to a higher energy level. The electron33
then has potential energy and is said to be in an excited state.
Shells or energy levels in an atom
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The quantum or photon of energy absorbed or emitted is the difference
between the lower and higher energy levels of the atom
ΔE = Ehigh – Elow = hν
where h is Planck’s constant and ν the frequency of a photon emitted or
absorbed energy.
vi) The angular momentum (mvr) of an electron orbiting around the
nucleus is an integral multiple of Planck’s constant divided by 2π.
Angular momentum =mvr = n h/2 π
where m = mass of electron, v = velocity of the electron, r = radius of the orbit ;
n = 1, 2, 3, etc., and h = Planck’s constant.
By putting the values 1, 2, 3, etc., for n, we can have respectively the angular
momentum, h/2 π 2h/2 π , 3h/3 π , etc. 34
There can be no fractional value of h/2π. Thus the angular momentum is said
to be quantized.
 Distribution of electrons in different shells

The distribution of electrons in the different shells was suggested by Bohr and

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Bury. The following are the rules for filling electrons in the different shells.

i) The maximum number of electrons in a shell is given by the formula 2n2

where n is the number of the shell 1, 2, 3 etc.
First shell or K shell can have = 2n2 = 2 x 12 = 2x1x1 = 2 electrons
Second shell or L shell can have = 2n2 = 2 x 22 = 2x2x2 = 8 electrons
Third shell or M shell can have = 2n2 = 2 x 32 = 2x3x3 = 18 electrons
Fourth shell or N shell can have = 2n2 = 2 x 42 = 2x4x4 = 32 electrons
and so on.

ii) Electrons cannot be filled in a shell unless the inner shells are filled.

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 BOHR’S POSTULATES: IN BRIEF

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Quantization of
Retained key
angular momentum.
features of
Rutherford’s nh
mvr 
model. 2

Energy emitted/absorbed when

electrons jump from one orbit to
another. E  E  E
f i
Concept of
stationary  h
circular orbits.
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 SERIES OF HYDROGEN SPECTRUM
(Bohr’s Explanation)

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 The solitary electron in hydrogen atom at ordinary temperature resides in
the first orbit (n = 1) and is in the lowest energy state (ground state).
When energy is supplied to hydrogen gas in the discharge tube, the electron
moves to higher energy levels viz., 2, 3, 4, 5, 6, 7, etc., depending on the
quantity of energy absorbed.

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From these high energy levels, the electron returns by jumps to one or
other lower energy level. In doing so the electron emits the excess energy as
a photon.
This gives an excellent explanation of the various spectral series of
hydrogen.
 Lyman series is obtained when the electron returns to the ground state
i.e., n = 1 from higher energy levels (n2 = 2, 3, 4, 5, etc.).

Similarly, Balmer, Paschen, Brackett and Pfund series are produced when
the electron returns to the second, third, fourth and fifth energy levels
respectively
as shown in Fig.
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SERIES OF HYDROGEN SPECTRUM
(Bohr’s Explanation)

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UV Visible

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8 IR IR IR
7
6
5 Pfund
4
Brackett
3
Paschen
2
Balmer
1 38
Lyman 
 SPECTRAL LINES IN HYDROGEN SPECTRUM

No. of spectral lines in

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n(n  1)
hydrogen spectrum 
2
n  Shell number

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Series ni nf Region
Lyman 1 2,3,4,5… Ultraviolet
Balmer 2 3,4,5….  Visible
Paschen 3 4,5,6….  Infrared
Brackett 4 5,6,7,8…  Infrared
Pfund 5 6,7,8…..  infrared

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 Rydberg’s Formula
Rydberg’s formula is used to explain spectral lines of
hydrogen like chemical elements.

Utilizing Bohr’s Postulates, it can be deduced that

the energy of a photon emitted by a hydrogen atom is
given by the difference of two hydrogen energy levels
:
The difference in energy between the levels n1 and
n2 is given by a Redberg’s equation as:

ΔE = En2- En1 =

As we know ΔE = hν = hc/λ

hc/λ =

where R is Rydberg constant. The value of R

1/ λ = ν = can be calculated as the value of e, m, h and c
OR are known. It comes out to be 109,679 cm– 1
and agrees closely with the value of Rydberg
1/ λ = ν = constant in the original empirical Balmer’s
equation (109,677 cm– 1).
 WAVELENGTH AND WAVE NUMBER IN TRANSITION

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The Bohr model was successful in determining where all the spectral lines 41
of H should be.
 Balmer Spectral Series

•The Balmer series is particularly useful

in astronomy because the Balmer lines appear in
numerous stellar objects due to the abundance of
hydrogen in the universe, and therefore are
commonly seen and relatively strong compared to
lines from other elements.

•The familiar red H-alpha spectral line of hydrogen

gas in the far right, which is the transition from the
shell n = 3 to the Balmer series shell n = 2, is one of
the conspicuous colors of the universe.
ILLUSTRATIVE PROBLEM
A gas sample of hydrogen atoms are shot with electrons of 12.75 eV
energy.What will be the energy of radiation emitted in Balmer

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series?
Solution Energy of an electron
in ground state  13.6 eV

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Energy of the excited electron
 12.75  (13.6)  0.85eV
 Energy level of the electron,
13.6  Z2
 0.85  
n2 n  4

For Balmer series,n1  2, n2  4

1 1  1 1 
 energy  13.6 Z  2  2   13.6  12  2  2 
2
n 
 1 n2  2 4 
 2.55 eV
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Drawbacks of Bohr’s Model

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Explains spectrum
of only hydrogen and
hydrogen like species
Does not explain
( single electron species) Stark effect and
Zeeman effect

No proof for
Not in accordance quantization of
with Dual nature angular momentum
and Heisenberg’s 44
uncertainty principle
 Bohr-Sommerfeld Model
When spectra were examined with spectrometers, each line was found to consist

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of several closely packed lines. The existence of these multiple spectral lines
could not be explained on the basis of Bohr’s theory.
Sommerfeld modified Bohr’s theory as follows:

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Bohr considered electron orbits as circular but Sommerfeld postulated the
presence of elliptic orbits also. An ellipse has a major and minor axis. A circle
is a special case of an ellipse with equal major and minor axis.

The angular momentum of an electron moving in an elliptic orbit is also

supposed to be quantized. Thus only a definite set of values is permissible. It is
further assumed that the angular momentum can be an integral part of h/2π units,
where h is Planck’s constant.
Or that, angular momentum = kh/2π
where k is called the azimuthal quantum number, whereas the quantum
number used in Bohr’s theory is called the principal quantum number. The
two quantum numbers n and k are related by the expression : 45
n/k = length of major axis/length of minor axis
 Bohr-Sommerfeld Model
• Bohr’s model does not work

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in case of heavier elements
where the spectral lines
observed did not corroborate
with the applied magnetic

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field. It was found that
spectral lines are not
homogenous but consists of Bohr’s Atomic Model
several convenient lines.

• Sommerfield proposed that

not only do electrons travel in
certain orbits but the orbits
have different shapes and the
orbits could tilt in the
presence of a magnetic field.
This explained well the 46
splitting of spectral lines Bohr-Sommerfield Model
observed for heavier elements
ADVANTAGES AND DISADVANTAGES OF BOHR-SOMMERFIELD
MODEL
• Somerfield's Model predicted the splits in
the spectrum. The electrons moving on the

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two orbits of the same n number but of
different shape have a bit different energies
which explained the splitting of spectral
lines or very closely spaced spectral lines.

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• Somerfield's Model also showed that orbits
don’t have to lie on the same plane and could
tilt in the presence of a magnetic field.

• The fundamental flaw was that

orbitals could tilt relative to xy plane
only in certain discrete values.
However, observation shows that an
atom can be tilted w.r.t x,y,z co-
ordinates without restriction. This flaw
is to be corrected by wave mechanics model 47
of Schrodinger.
 Dual Nature
(de-Broglie equation: Einstein has suggested in 1905, that light has dual character as

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wave and also as particle. Louis de-Broglie proposed that electron ( or matter) also has
a dual character, as wave and as particle.

de Broglie Matter has both wave

According to Planck’s
and particle nature.
quantum theory
E  h (1)
According to Einstein’s equation
E  mc2 (2)
Equating (1) and (2) mc2  h de Broglie
c h wavelength
mc2  h  
 mc
h
For any particle =
mv 48
de Broglie cont………….

Replacing c by velocity (v) of electron we have

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λ = h/mv = h/p

Where p = momentum of electron

de Broglie equation is applicable only for small particle like electrons

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etc. and has no significance for large particle

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HH ’SUUNCERTAINITY
EISENBERG’S
EISENBERG NCERTAINTY PPRINCIPLE
RINCILE
• It is impossible to know both the position and
momentum exactly, i.e., x=0 and p=0

• These uncertainties are inherent in the physical

world and have nothing to do with the skill of the
observer

• Because h is so small, these uncertainties are not

observable in normal everyday situations

x.p  h / 4
 ANOTHER CONSEQUENCE OF
HEISENBERG’S UNCERTAINTY PRINCIPLE

 A quantum particle can never be in a state of rest, as this

would mean we know both its position and momentum
precisely

 The more accurately we know the energy of a body, the

less accurately we know how long it possessed that
energy
 HEISENBERG’S UNCERTAINTY PRINCIPLE

The position and momentum of a subatomic particle cannot be

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determined simultaneously and with absolute accuracy.

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x.p 
4

h
x.v  Since p=mv
4m

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ILLUSTRATIVE EXAMPLE
Calculate the uncertainty in position of an electron whose velocity is
3 x 104 cm s-1 accurate up to 0.001%. Mass of an electron = 9.1 x 10-28 g.

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Solution Heisenberg’s uncertainty principle

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h
 x × p =
4
h
x × mv =
4

3  104  0.001
v   0.3 cms1
100

6.626  1027
x =
4  3.14  9  10 28  0.3

x = 1.95 cm 53
 Quantum Numbers

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The principal quantum number n governs the
electron's energy and average distance from the
nucleus.

The orbital quantum number l determines the

magnitude of an atomic electron's angular momentum.

The magnetic quantum number ml specifies the

direction of an atomic electron's angular momentum.

The spin magnetic quantum number ms of an atomic

electron has two possible values, +1/2 or -1/2,
depending on whether the electron aligns itself along a54
magnetic field (+1/2) or opposite to the field (-1/2).
 Quantum Numbers

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principal quantum number n 1,2,3,…..
orbital quantum number l 0,1,2,….n-1
magnetic quantum number m -l to +l
for n=2 -2,-1,0,1,2
spin magnetic quantum number +½ or –½ spin

To know where or what state the electron is in you need to

know the four quantum numbers.

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ORBITALS
Orbitals are regions in space where an electron is likely
to be found:
 90% of the time the electron is within the boundaries
described by the electron density map
 The exact path of an electron in a given orbital is not
known!

DESCRIBING ORBITALS
Use quantum numbers to describe orbitals. A given
orbital can be described by a set of 3 quantum numbers:
1. Principal quantum number (n)
2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)

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PRINCIPAL QUANTUM NUMBER (N)
(n) describes the size and energy of the orbital:
 Possible values: whole number integer
1, 2, 3, …
 As “n” increases so does the size and energy of the
orbital

ANGULAR MOMENTUM QUANTUM NUMBER (L)

(l) is related to the shape of the orbital:
 Possible values: (l) is an integer between 0 and n-1
 Each (l) value is also assigned a letter designation

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ANGULAR MOMENTUM QUANTUM
NUMBER (L)

(l) Value Letter Designation

0 s

1 p

2 d

3 f
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n Possible Designation
l values
1 0 1s
2 0 2s
1 2p
3 0 3s
1 3p
2 3d

4 0 4s
1 4p
2 4d
3 4f
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 MAGNETIC QUANTUM NUMBER (ML)
(ml) is related to the orientation of the orbital in 3-D space:
 Possible values: - l to + l

Consider the p orbital…it has an l value of 1 and

thus the possible ml values are -1, 0, +1

 These 3 ml values correspond to the 3 possible

orientations of the p orbital

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ML AND ORBITALS

l ml # orbitals

0 (s) 0 1

1 (p) -1, 0, 1 3

2 (d) -2, -1, 0, 1, 2 5

3 (f) -3, -2, -1, 0, 1, 2, 3 7

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QUANTUM NUMBER SUMMARY
 A set of 3 quantum numbers describes a specific orbital
 Energy and size - n
 Shape - l

 Orientation – ml

4TH QUANTUM NUMBER!

A 4th quantum number was added to describe the spin
on a given electron.
 Called the electron spin quantum number - ms
 Possible values: +1/2 and -1/2

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 STERN-GERLACH EXPERIMENT

The Stern–Gerlach experiment involves sending a beam of particles

through an inhomogeneous magnetic field and observing their deflection.
The results show that particles possess an intrinsic angular momentum that
is most closely analogous to the angular momentum of a classically
spinning object, but that takes only certain quantized values (ie is not
continuous).
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THE S-ORBITAL
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65
P-ORBITALS
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66

The d orbitals
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67

The f orbitals
Principles and rules to write the
electronic configuration

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1. Aufbau principle

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2. Pauli’s exclusion principle

3. Hund’s rule of maximum multiplicity

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 AUFBAU PRINCIPLE

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In German, "Aufbau" means "construction" (also Aufbau rule or
building-up principle), is used to determine the electron
configuration of an atom, molecule or ion.

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The principle postulates a hypothetical process in which an atom is
"built up" by progressively adding electrons

According to the principle, electrons fill orbitals starting at the lowest

available (possible) energy states before filling higher states (e.g. 1s
before 2s).

The order in which these orbitals are filled is given by the n+ rule,
where orbitals with a lower n+ value are filled before those with
higher n+ values.

For the same n+ value, those with lower n values will be filled first.

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Order for Filling Atomic Subshells
n+  =1

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n+  =2
n+  =3

n+  =4

70

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Order for Filling Atomic Subshells

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 PAULI’S EXCLUSION PRINCIPLE

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In an atom no two electrons can have the same
set of four quantum numbers.

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different
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No. Values Max No.
Sub
Electron
Shell Orbitals (-l to +l)

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s

s (l = 0) 1 (0) 2

p (l = 1) 3 (-1, 0, +1) 6

d (l =2) 5 (-2,-1,0,+1,+2) 10

f (l =3) 7 (-3,-2,1,0,+1,+2,+3) 14

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 HUND’S RULE OF MAXIMUM MULTIPLICITY

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Among the orbitals of same energy, electrons do not start pairing, until all
these orbitals are singly occupied”.

Hund’s rule is also called as the principle of minimum pairing and the
principle of maximum multiplicity.

Case - 1 1s2 2s2 2px1 2py1 2pz1

2px2 2py1 2pz1

Case - 2 1s 2s2
2

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 GROUND STATE ELECTRON CONFIGURATION OF ELEMENT

Each electron shell can hold a maximum of 2n2 electrons where n

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is the shell number

These electrons are accommodated in s, p, d and f orbitals, the

maximum number of electrons in each type of orbitals being

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determined by its electron-holding capacity (for s = 2, p = 6, d = 10
and f = 14)

In the ground state of an atom, the electrons tend to occupy the

available orbitals in the increasing order of energies, the orbitals
of lower energy being filled first

Any orbital may have one or two electrons at the most

When several orbitals of equal energy (degenerate orbitals) are

available, electrons prefer to occupy separate orbitals rather than
getting paired in the same orbital
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 SCHRODINGER WAVE EQUATION

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Describes the probability of finding an
electron in a given volume element.

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2  2  2 8 2m
   (E  V)   0
2 2 2 2
x y z h

2  Probability of finding the electron in a given region.

  Describes the wave motion of the electron.

Schrodinger’s equation can only be solved exactly for the hydrogen atom.
approximations have to be made to solve it for multi-electron systems.
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 The Schrodinger Equation

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Solving this equation will give us
• the possible energy levels of a system (such as an atom)
• The probability of finding a particle in a particular region of space

It’s hard to solve this equation. Therefore, our approach will be to learn
about a few of the simpler situations and their solutions.
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PARTICLE IN A BOX

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Rigid walls Potential energy
Newton’s view function U(x)

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 THE PARTICLE IN A BOX IS NOT FREE,

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IT IS “BOUND” BY U(X)

Examples: An electron in a long molecule or in a straight wire

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To be a solution of the SE, (x)
has to be continuous
everywhere, except where U(x)
has an infinite discontinuity

“Boundary conditions”:
(x) = 0 at x=0, L and all values of x outside this 79
box, where U(x) = infinite
 SOLUTIONS TO THE S.E. FOR THE PARTICLE
IN A BOX

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d/dx also has to be
continuous everywhere,

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(except where U(x) has an
infinite discontinuity) because
you need to find d2/dx2

Normal modes of a vibrating string! 80

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From 0 < x < L, U(x) = 0, so in this region,
(x) must satisfy:

d2 2
 2
 E  (x)
2m dx
Same as a free particle?!?!?!?!?
81
 You may be tempted to conclude that

 (x)  Ae ikx

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, the solution for a free particle, is a
possible solution for the bound one too.

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WRONG!!!!
Why not?
The above (x) does NOT satisfy the boundary conditions that
(x) = 0 at x=0 and x=L.

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 30 April 2019
SO WHAT IS THE SOLUTION THEN?
Try the next simplest solution, a superposition of two waves

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 (x)  A1e  A2e ikx ikx

2 2
k
The energy again is E
2m
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WAVE FUNCTIONS FOR THE PARTICLE IN
A BOX

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(x) = 0

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THE ENERGY OF A PARTICLE IN A BOX
CANNOT BE ZERO!

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You could try to put n = 0 into this equation, but then
(x) = 0, which would mean there is no particle!

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The function (x) = C sin(kx) is a solution to the Schrodinger Eq. for the
particle in a box

Probability distribution function

Wave function

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INFINITE SQUARE-WELL POTENTIAL
 The simplest such system is that of a particle trapped in a box
with infinitely hard walls that the particle cannot penetrate. This
potential is called an infinite square well and is given by

 Clearly the wave function must be zero where the potential is

infinite.

 Where the potential is zero inside the box, the Schrödinger wave

equation becomes where .

 The general solution is .

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QUANTIZATION

 Boundary conditions of the potential dictate that the wave function

must be zero at x = 0 and x = L. This yields valid solutions for integer
values of n such that kL = nπ.

 The wave function is now

 We normalize the wave function

 The normalized wave function becomes

 These functions are identical to those obtained for a vibrating string

with fixed ends.
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QUANTIZED ENERGY
 The quantized wave number now becomes
 Solving for the energy yields

 Note that the energy depends on the integer values of n. Hence

the energy is quantized and nonzero.
 The special case of n = 0 is called the ground state energy.

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SIMPLE HARMONIC OSCILLATOR
 Simple harmonic oscillators describe many physical situations: springs,
diatomic molecules and atomic lattices.

 Consider the Taylor expansion of a potential function:

Redefining the minimum potential and the zero potential, we have

Substituting this into the wave equation:

Let and which yields .

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PARABOLIC POTENTIAL WELL

 If the lowest energy level is zero, this violates the uncertainty principle.
 The wave function solutions are where Hn(x) are Hermite
polynomials of order n.

 In contrast to the particle in a box, where the oscillatory wave function is a

sinusoidal curve, in this case the oscillatory behavior is due to the polynomial,
which dominates at small x. The exponential tail is provided by the Gaussian
function, which dominates at large x. 91
ANALYSIS OF THE PARABOLIC POTENTIAL WELL

 The energy levels are given by

 The zero point energy is called the Heisenberg

limit:

 Classically, the probability of finding the mass is

greatest at the ends of motion and smallest at the
center (that is, proportional to the amount of time
the mass spends at each position).
 Contrary to the classical one, the largest
probability for this lowest energy state is for the
particle to be at the center. 92
A diatomic molecule vibrates somewhat like two masses on a spring with
a potential energy that depends upon the square of the displacement from
equilibrium. But the energy levels are quantized at equally spaced values.
The energy levels of the quantum harmonic oscillator are and for a
diatomic molecule the natural frequency is of the form

where the reduced mass is given by

m1m2
m
m1  m2

This form of the frequency is the same as that for the classical simple
harmonic oscillator. The most surprising difference for the quantum case
is the so-called zero-point vibration" of the n=0 ground state. This implies
that molecules are not completely at rest, even at absolute zero
temperature.
The quantum harmonic oscillator has implications far beyond the simple
diatomic molecule. It is the foundation for the understanding of complex
modes of vibration in larger molecules, the motion of atoms in a solid
lattice, the theory of heat capacity, etc. In real systems, energy spacings
are equal only for the lowest levels where the potential is a good
approximation of the "mass on a spring" type harmonic potential. The
93
anharmonic terms which appear in the potential for a diatomic molecule
are useful for mapping the detailed potential of such systems.