SATHYABAMA

INSTITUTE OF SCIENCE AND TECHNOLOGY

• COURSE CODE: SCYA1102

COURSE NAME: ENGINEERING CHEMISTRY
• I B.E CSE D1 (2021 – 2025)
COURSE INSTRUCTOR
Dr. T. KRITHIGA
ASSOCIATE PROFESSOR
DEPARTMENT OF CHEMISTRY
SYLLABUS
Total
L T P Credits
SCYA1101 ENGINEERING CHEMISTRY Marks
3 1 0 4 100

UNIT 1 – BONDS TO BANDS

UNIT 2 – MOLECULAR SPECTROSCOPY
UNIT 3 – FUNCTIONAL MATERIALS
UNIT 4 – CARBON MATERIALS FOR HEALTH, STEALTH AND ENERGY
UNIT 5 – ENGINEERING MATERIALS
UNIT 1 BONDS TO BANDS
• Introduction to quantum chemistry

• Motion of a quantum mechanical particle in one dimension (time- independent)

• Schrödinger wave equation for hydrogen atom (No derivation)

• Physical meaning of wave function - Angular and radial wave functions and probability densities

• Quantum numbers

• Principal, azimuthal, spin and magnetic quantum numbers

• Wave functions and orbital shapes - s,p,d,f

• LCAO-MO of H2

• Band theory of solids: Conductors, semi-conductors and superconductors

• Role of As and Ga doping on band structures.

UNIT 2 MOLECULAR SPECTROSCOPY
• Electromagnetic spectrum
• Interaction of radiation with matter
• Energy levels in molecules
• Microwave spectroscopy
• Principle
• Classification of molecules based on moment of Inertia
• Rotational energy expression (J levels)
• Calculation of J for CO molecule
• Vibrational spectroscopy
• Normal modes of vibrations
• Vibrations of polyatomic molecules (CO2 and H2O)
• Determination of Force constant
• Electronic transitions in organic molecules
• Mathematical derivation of Beer- Lambert’s law
• Stimulated Emission
• Lasers in action
• Excimer laser, Diode laser and Gas laser.
UNIT 3 FUNCTIONAL MATERIALS
• Introduction to conducting polymers

• Charge transport carriers: Exciton formation in organic solar cells and organic light emitting diodes
(principle and working)

• Conduction mechanism in polymers: Soliton, polaron and bipolaron formation in polyacetylene and
polyaniline

• Liquid crystals: Characteristic features and phases of liquid crystals

• Liquid crystal displays.

UNIT 4 CARBON MATERIALS FOR HEALTH,
STEALTH AND ENERGY
• Introduction to carbon materials

• Fullerenes – Production, properties and applications

• VanderWaal’s solid

• Structure of graphene, graphene oxide and reduced graphene oxide

• Mechanical and electrical properties of graphene

• Graphene based energy storage devices for space applications

• Carbon nanotubes – Single-walled and multiwalled CNTs

• Synthesis of CNTs by Thermal CVD and laser ablation method

• Electrical and mechanical properties of CNTs

• Applications of CNTs.
UNIT 5 ENGINEERING MATERIALS
• Phase equilibria:

• Gibbs phase rule

• Terms involved in Phase rule

• Phase diagram of water system

• Thermal method of analysis

• Construction of simple eutectic system (Lead-Silver system).

• Fuels:

• Classification of fuels

• Determination of calorific values of solid fuels by bomb calorimeter

• Manufacture of synthetic petrol by Fischer-Tropsch method

• Knocking in IC engines – Chemical structure – Octane and cetane rating of fuels.

• Nanomaterials:

• Size dependent properties of nanomaterials

• Synthesis of gold and silver nanoparticles by Chemical reduction method

• Applications of nanoparticles in medicine.

Chemistry involved in Mobile Phone
• GUESS?
NRAM
• New type of non-volatile memory known as Nano-RAM (NRAM) -- it's
based on carbon nanotube (CNT)
Foldable Mobile phone
• Organic LED- Flexible and mixed with ITO
UNIT-1 BONDS TO BANDS
BONDS IN COMPOUNDS
BANDS IN CHEMISTRY
Band theory of solids
MATERIALS

Conductors
and Insulators Semiconductors
Electromagnetic Spectrum (EM)

The electromagnetic (EM) spectrum is the range of all types of EM radiation

The electromagnetic spectrum is the range of frequencies (the spectrum) of electromagnetic
radiation and their respective wavelengths (or frequency) and photon energies.
RFID
• Radio-frequency identification (RFID) uses electromagnetic
fields to automatically identify and track tags attached to
objects.
LPR – License Plate Recognition
Image processing Recognition – Infra red
Radiation image
• LPR is also called in different references as:
• Automatic Vehicle Identification (AVI)
• Car Plate Recognition (CPR)
• Automatic Number Plate Recognition (ANPR)
• Car Plate Reader (CPR)
• Optical Character Recognition (OCR) for Cars

Source: http://www.licenseplaterecognition.com
Electromagnetic Wave (EM)

Source: https://commons.wikimedia.org/wiki/File:EM-Wave.gif
 ElectroMagnetic Radiation (EMR)
• Electromagnetic radiation is a form of energy that is produced
by oscillating electric and magnetic fields perpendicular to
each other, traveling through a vacuum or matter at constant
velocity
• CHARACTERISTICS OF EMR
• Wavelength (λ): The linear distance between successive crests
or trough of a wave is known as wavelength. It is usually
expressed in centimetre or millimetres.
• Frequency (ν): The number of vibrations or oscillations per
second is known as frequency. It is expressed in Hertz.
• Wave number (ῡ ): The reciprocal of wavelength is known as
wave number. It is expressed in cm-1 .
• Energy of EMR (E): Electromagnetic radiations consist of
particles having small packets of energies called quanta or
photons.
• Photons possess the characteristic of wave and travel with the
speed of light. The amount of energy corresponding to one
photon is expressed by Planck’s equation as E
• E = hν or E = hc/λ or E = hcῡ
• where h – Planck’s constant (6.62x10-34J)
• ν - frequency in Hz
• λ – wavelength in cm
• c – Velocity of light m/s

Source: https://gfycat.com/ickyfilthybobolink
• Two waves of the same frequency are in phase if they cross the x axis
at the same point in the same direction, otherwise they are out of
phase.
Why an object looks colour?
• A green leaf absorbs almost all wavelengths except the green
wavelength range between 500 nm and 550 nm.
• Thus, the reflected light contains exactly the wavelength range that
gives the green colour

Source: www.tec-science.com
What is a Black body?
• An object absorbs all incident wavelengths of visible light, then obviously no visible radiation
is reflected.
• The object appears black to us under normal conditions.
• A black object therefore does not emit any visible radiation.
• An object that absorbs all incident radiation is therefore also called a blackbody (or black
body).
• A perfect black body, however, only exists in the ideal conception.
• In reality, every object will always reflect a part of the incident radiation.

Source: www.tec-science.com
What is a black body radiation?
• Even if by definition a blackbody absorbs
all incident radiation, it still emits
radiation.
• Only if the temperature is increased very
strongly and the body starts to glow,
radiation in the visible wavelength range is
emitted.
• Even if the body now has a color, this
object is still called a blackbody
• So a blackbody does not necessarily have
to be black!
• An impressive example is the sun.
• In fact, the sun is almost perfect black
body.
• Only due to the enormous temperature of
5778 K it appears incandescent in the sky.
Source: www.tec-science.com
Thermal radiation of a light bulb at
different temperatures

Source: www.tec-science.com
BLACK BODY RADIATION
• A blackbody is an idealized object that absorbs all incident electromagnetic radiation
• An ideal black body is an object that absorbs all the radiations falling on it.
• A hollow enclosure or chamber having a small hole is an appropriate black body because it absorbs all the
radiation entering it due repeated reflections inside the enclosure.
• The radiation emitted from such a black body is called black body radiation.
• A perfect absorber is also a perfect emitter of radiation.
• The intensity of the total radiation emitted per unit surface area from a black body depends on temperature
T and is independent of the nature of the solid.

Source: http://www.pa.uky.edu/~shlosman/anim/bb.html
Laws of Radiation
Planck’s law of radiation

Source: https://sites.google.com
Planck’s quantum theory of radiation

• According to this theory Max Planck

• Energy is absorbed or emitted in the form of discrete sets of small bundles of
energy known as quanta.
• Each quantum is associated with certain amount of energy E = hν, where h is
Planck constant and ν is the frequency of radiation.
• A body can emit or absorb energy only in integral multiples of quantum (i.e) 1hν,
2hν, 3hν………nhν
Photoelectric Emission
• In 1905, based on the Planck’s idea of energy quantization,
Albert Einstein discovered law of the photoelectric effect.

Source: https://makeagif.com

Source: https://meded.psu.ac.th
Photoelectric Effect
Observations

1.Light with minimum frequency called the threshold frequency ν0 is necessary to cause emission of electron
by photoelectric effect. If ν > ν0 there is photoelectric effect occurring

If ν < ν0 there is no photoelectric effect

2. Kinetic energy of emitted electrons is directly proportional to frequency and independent of intensity of
incident radiation.

Source: https://makeagif.com
Properties of electrons

• Particle Property
• Electrons possess negative charge (e-)
• Electrons possess Mass (m)
Source: https://www.baumer.com
• Electrons possess Kinetic energy
• Electrons has Momentum (P=mv)
• Wave Property
• Electrons can be polarized
• Electrons can be diffracted

Source: https://gfycat.com
WAVE – PARTICLE DUALITY OF ELECTRON – de BROGLIE’S HYPOTHESIS
de BROGLIE’S HYPOTHESIS
• According to de-Broglie hypothesis, the subatomic particle like electron have both wave and particle nature
and de Broglie proposed that the wavelength or frequency of electron similar to the photon is related to the
momentum of the electron

• where λ = wavelength of electron, m = mass of electron, p = momentum of electron, h = Planck’s constant.

• de Broglie hypothesis of wave-particle duality is applicable to all subatomic particles such as neutrons,
protons etc.

Source:
Uncertainty in Position and Momentum

Source: https://chem.libretexts.org
 Heisenberg Uncertainty Principle
• Heisenberg stated that “it is not possible, even in principle to measure both
position and momentum of an electron simultaneously”. This is known as
Heisenberg uncertainty principle.
• Mathematically it is expressed as

• Where
• ∆x is the uncertainty in position of the electron,
• ∆p is the uncertainty in momentum of the electron Werner Heisenberg
• h is the Planck’s constant.
• If the position of an electron is determined with high accuracy then its
momentum becomes uncertain.
• Similarly, if the momentum of the electron is measured precisely then its
position will be uncertain.
• This principle holds good only for microscopic particles.
• However, it does not apply to larger bodies (i.e) both momentum and
position can be determined accurately at the same time.

Macroscopic Particles (Larger bodies)

• The more accurately a particle’s position is known (the smaller Δx is), the less accurately the momentum of
the particle in the x direction (Δpx) is known.

• Mathematically, this occurs because the smaller Δx becomes, the larger Δpx must become in order to satisfy
the inequality.

• However, the more accurately momentum is known the less accurately position is known

Source: https://www.algorithm-archive.org
Solved Problems
• When a radiation of wavelength 500 nm strikes a metal surface, electrons are emitted from the surface of a
metal. The kinetic energy for one electron emitted from the metal is 1x10-19J. Calculate the minimum energy
required to remove an electron from a metal (binding energy).
Solution:

Wavelength λ =500 nm

Kinetic Energy = 1x10-19 J

Incident radiation energy

The minimum energy required to remove an electron from a metal is

Solved Problems
• Calculate the wavelength of an electron having velocity 6 x 106 ms-1and mass 9.1 x 10-31 Kg.
• Solution: According to de- Broglie hypothesis, the wavelength of an electron
Solved Problems
• Calculate the uncertainty in position for a ball of mass 0.2 Kg moving with a speed of 10 ms-1 is measured at
an accuracy of 1%.
• Solution: The momentum of the ball is given by

• Thus uncertainty in momentum is calculated from momentum and % of accuracy

THEORY OF WAVE MOTION
• The de Broglie, Heisenberg uncertainty principle and electron diffraction experiments established the dual nature
of electrons as particle as well as wave.
• A particle is localized and it cannot be present in more than one place at same time whereas wave cannot be
localized at a point and varies from a point to point in space.
• In order to insight the behaviour of electrons it is necessary to understand the characteristics of wave motion.
• Classical Waves and Wave Equation
• Consider the wave motion in vibration of a string, the vertical displacement of string from its mean position and is
called the amplitude of wave or vibration.
• This amplitude is a function of position (x) and time (t) and denoted as Ψ(x,t)
• Here the wave makes same amplitude at regular intervals of ∆x which is λ the wavelength of the wave.
• The velocity of wave c is given by λ/t, the frequency ν (number of waves per unit time) will be
• c = λ/t
• 1/t = c/λ
• ν = c/λ
• Wave number (number of waves per unit distance) will be ῡ = 1/λ

Classical wave (Running wave)

• The periodic nature of Ψ(x,t) propose the sine or cosine function of x and t where x is position coordinate
and t is time coordinate.

• where Ψ=Ψ(x,t). By applying separation of variables method, function Ψ(x,t) is separated into a product of
two functions
•
• where Ψ(x) is a function of x only and Φ(t) is a function of t only. Substituting equation (2) in (1)

• The left hand side of equation (3) depends only on x and right hand side depends only on t however both
sides are equal and are equated to a constant -k2
• Thus two equations are obtained from equation (4)

• Here equation (5) is the time-independent wave equation called as amplitude equation.
• The general solutions for equations (5) and (6) are

• where A,B,C and D are arbitrary constants.

Classical Waves and Wave Equation
Stationary wave and Running wave

Source: https://www.flippingphysics.com
Stationary Waves
• Waves expressed by the equation (5) are called running waves in which Ψ is a function of time. However,
electron waves in atoms and molecules are stationary waves in which Ψ does not change with time. A
classical example of such wave is the wave in a vibrating string clamped at two ends.
• Thus equation (5) may be expressed as

• From classical waves we know that

• Equation (7) becomes

• Hence the wave does not vibrate at the ends x = 0 and x = L and this is called as boundary conditions.
• Boundary conditions:
• The first boundary condition x = 0, Ψ becomes 0 from equation (12) and B becomes zero (B = 0)
Stationary wave - Vibration in clamped string
Schrodinger Equation for Particle Waves
Conditions for Acceptable Wave Function

• The conditions for an acceptable wavefunction Ψ are

• It must be finite.
• It must be single-valued at all points.
• It must be continuous.

• If these three conditions are obeyed then the function Ψ is called a well-behaved
wave function.
Motion of Quantum Mechanical Particle

• The quantum mechanical particle such as electrons in atoms and molecules

can execute translational, rotational and vibrational motion.
• The common type of motion is translational or linear when they move freely.
• For linear motion of free particle which is not affected by any force or
potential barrier and free to move in limitless space becomes Schrodinger
equation for free particle and is given by

• Here potential energy V is a constant and assumed to be zero since the free
particle is not subjected to any potential barrier.
Motion of Quantum Mechanical Particle
Particle in one dimensional box
• Consider a particle is moving in a limited space like bounded electrons in atoms and
molecules serves as particle in a box model.
• If the limited space is a one dimensional box of length L with infinite high walls at the
two ends, the particle is not subjected to any force inside the box where potential
energy V = 0 and outside the box it is infinity thus V = ∞.
∞ ∞

V=∞ V=0 V=
∞
m

x=0 x=L
x
Source: https://en.wikipedia.org
• Hence the potential energy is discontinuous (high at x = 0 and x = L and inside the box is
zero), thus the Schrodinger equation should be considered inside and outside the box
separately.
• The Schrodinger equation outside the box (where V = ∞) will be

• The Schrodinger equation inside the box 0 ≤ x ≥ L (where V = 0)

• The probability of finding a particle outside the box, (i.e) Ψ2 = 0 due the large potential energy (V =
∞) present in these regions x < 0 and x > L and thus Ψ = 0.
• Since Ψ must be continuous (i.e) it cannot rise and fall suddenly thus Ψ must be zero at x = 0 and x =
L. This is the boundary condition for this system.
• The Schrodinger equation inside the box is written as

• The equation is satisfied by well behaved functions such as sin kx, cos kx, eikx and e-ikx
• Wave function and Energy of the particle
• The wave function is described either in terms of real form such as sin kx and cos kx and
complex forms such as eikx and e-ikx
• The general solution of real form of wave function is given as

where A and B are arbitrary constants. The values of A, B and k are determined by applying
boundary conditions to above equation
• At x = 0, Ψ becomes 0

Thus B = 0
• At x = L, Ψ becomes 0

Thus 0 = A sin kL
Sin KL = Sin nπ
This expression is satisfied if either A = 0 or kL = nπ.
Sin KL = 0
• Case 1: If A = 0, B = 0, then Ψ becomes 0 everywhere which not acceptable.
• Case 2: Thus kL = nπ or k = nπ/L where n is an integer (1,2,3…) but not zero (if n = 0, Ψ becomes 0)
• The wave function and energy of the particle in one dimensional box is given as
Quantization and Energy levels
• Quantization • Energy levels
• In the energy equation, • The figure shows the quantization of energy of a
particle in one dimensional box.
• The allowed energy levels are drawn as horizontal
the terms h, m and L are constants and energy E depends lines which shows that for a value of n, energy E
only on integer n. does not change with position x of the particle.
• Thus energy is quantized (i.e) have discrete set of values and • The lowest energy level E1 is not zero but
the integer n is a quantum number.
(n = 1) and is also called the “zero
• Hence a particle confined to move in a limited space and its
energy is quantized. point energy”.
• The energy E depends on n2 which shows that
∞ ∞ increase in n, increases the spacing between
n=4 energy levels

n=3 • Since E is proportional to

Energy

• Case 1: when the box is small the energy spacing

n=2 (∆E) is greater (i.e) the quantization is pronounced.
• Case 2: when the box is wider, ∆E decreases and in
n=1 limiting case of L⟶∞ (free particle) the
quantization vanishes.
x=0 x=L • Similarly ∆E is also proportional to
x thus for macroscopic system (large m) the energy
levels are closely spaced and there is no
quantization.
Value of A
• The value A is determined by the normalization of wave function which
is given by

• Thus the normalized wave function is

Solved Problems
• Calculate the zero point energy of an electron of mass 9.1 x 10-31Kg in one dimensional box of length 1Å.
• Solution: The energy of electron in one dimensional box is

• The zero point energy is the lowest energy level or first energy level
Solved Problems
• Calculate the energy difference between E4 and E3 for an electron in a one dimensional box of length 12Å.
• Solution: The energy of electron in one dimensional box is

• The electron in lowest energy level or first energy level

• The energy difference between E4 and E3 for an electron

Physical meaning of wave function Ψ- Probability density
Probability density curves of particle in one dimensional box for n = 1and n = 2 energy levels

Source: https://bouman.chem.georgetown.edu
Schrodinger equation for hydrogen atom
Relationship between Cartesian and spherical coordinates

• The Cartesian coordinates are converted to spherical coordinates in terms of radius r and angle φ measured
between 0 to 2π and angle θ measured between 0 to π. The relationship between x, y and z and r, θ and φ is
given as
• This equation can be separated into spherical harmonic function Y(θ,φ) and radial function R(r) by
using product wave function.

• The spherical harmonic functions give the information about the position of electron around the
proton
• The radial function R(r) tells the distance of electron form the proton.
• The energy term En and the solution for R(r) and Y(θ,φ) depends only on one quantum number n
(principal quantum number).
• However, the other three quantum numbers are necessary for proper description of complete
wave function.
QUANTUM NUMBERS
• Four quantum numbers are necessary to define an orbital.
• The combination of these four quantum numbers of electrons in an atom is described by a wave
function satisfied by Schrodinger equation.
• The quantum numbers are used to account for the electronic configuration of an electron in an
atom and the probable position of electron in an atom.
• The quantum numbers explain the shells, subshell, orbitals and spin of electrons.
• The four quantum numbers are
• Principal quantum number (n)
• Azimuthal quantum number (l)
• Magnetic quantum number (ml)
• Spin quantum number (ms)
Principal quantum number (n)

• The principal quantum number characterizes the principal electron shell which decides the
energy of an electron and the probable position of the electron from the nucleus.
• Thus n describes the size of the orbital and energy level in which the electron is placed.
• The larger the value of n, larger is the size of orbital which show that the electron is at longer
distance from the nucleus.
• When n = 1, it belongs to first principal shell (ground state) and lowest energy level.
• When electron absorb energy it is excited to the higher principal shells (n = 2,3,4,…).
• Thus n takes integral values 1,2,3…∞ except zero since when n = 0, the energy of atom becomes
zero and the atom doesn’t exists.
• The value of n describes the shells K, L, M, N…. in the atom.
Azimuthal quantum number (l)
• The azimuthal quantum number or orbital quantum number characterize the shape of the orbital
and the subshell to which electron belong to.

• Each l value indicates subshell which is designated as s, p, d, f.

• Each subshell corresponds to unique shape.

Source: https://chemed.chem.purdue.edu
• It also determines the number of angular nodes of the orbital which will be equal to the number
of l values.

• The value of l is subshell to which electrons belong to and it depends on n values and can have
integral values from 0 to n-1. Thus

l = 0, 1, 2…. (n-1).
Magnetic quantum number (ml)
Spin quantum number (ms)
• The spin quantum number refers the direction of spin of an electron in
an orbital. The direction of spin can be clockwise (ms = + ½) or
anticlockwise (ms = - ½)

Source: https://www.stickmanphysics.com
Source: https://web.fscj.edu
ASSIGNING ELECTRONS TO ORBITALS
• Three set of rules govern the filling of electrons in the orbital. They are
• Aufbau principle
• Aufbau principle states that the electrons in an atom occupy the orbital of lowest energy before filling the
higher energies. Thus electrons are filled in increasing order of energy
• 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s,…..

Source: www.toppr.com
Pauli-Exclusion principle
• It states that no two electrons in the same atom can have all the four quantum number the same.
• The electrons in each orbital have three quantum numbers n, l and ml same but the fourth quantum number ms
will be different.
• Thus a single orbital can accommodate a maximum of two electrons with opposite spin.
• The s-orbital can accommodate 2 electrons, p-orbital can hold till 6 electrons (each 3 orbitals hold 2
electrons), the five d-orbitals can accommodate 10 electrons and seven f-orbitals can hold 14 electrons.
 Hund’s rule
• According to Hunds rule, every orbital in a subshell should be filled with atleast one electron
before pairing of electrons takes place.
• The electrons in singly filled orbitals of subshell have the same spin.
ANGULAR AND RADIAL WAVE FUNCTIONS

• Thus the complete wave function of hydrogen-like atoms is given as

• Each wave function has two parts the radial wave function Rnl(r) and angular wave function
(spherical harmonics) Ylm(θ,φ).
• The radial wave function depends on the quantum numbers n and l
• The radial wave function describes the size of the atomic orbital (i.e) the distance between the
electron and nucleus.
• The angular wave function depends on only l and m.
• The angular wave function describes the shape of the atomic orbital.
Radial, Angular wave function and complete wave function of s and p
orbitals
The real forms of radial and angular wave functions and complete wave function for s and p orbitals of
hydrogen atom (Z = 1 and a0 = 1) is given below
WAVE FUNCTION OF ATOMIC ORBITALS
• The wave function Ψ(r,θ,φ) of hydrogen atom is known as atomic orbitals.
• Atomic orbital is a wave function that explains the behavior of an electron in atom or region of space.
• Orbital of different systems varies only with nuclear charge Z.
• The probability of finding an electron in atom is described by Ψ2 (square of wave function of atomic orbital).
Orbital Shapes
• Each orbital is represented by a number and a letter

• The number (1, 2, 3, …) indicates the energy level of the electron in the atom

• The letter (s, p, d, f) denotes the shape of the orbital.

• From the solution of Schrodinger wave equation, diagrammatic representation of

shapes of atomic orbitals is drawn using the boundary surface diagrams.

• A boundary surface diagram is a boundary surface for an orbital represented in a

space where the value of probability density Ψ2 is a constant.
 s-orbital
• Boundary surface diagram of s-orbital is spherical with nucleus at the center.
• All the s-orbitals 1s, 2s, 3s,… are spherically symmetrical but their size and energy increases with increase in
principal quantum number (n) values (1s< 2s< 3s…..).

Boundary surface diagram of s-orbital

 p-orbital
• Boundary surface diagram of p-orbital show two lobes on either side of plane passing through the center of
the nucleus called nodal plane that bisects the two lobes.
• Unlike s-orbital, the p-orbital has three orientations that are designated as px, py and pz which lie on x, y, z
axes which are mutually perpendicular to each other.
• These three p-orbitals have same energy, size and shape. The size and energy of the p-orbital increase with
increase in n values (2p< 3p< 4p…).

Nodal planes and Boundary surface diagram of p- orbitals

 d-orbital

Nodal planes and Boundary surface diagram of d-orbitals

f-orbital
• When n = 4 and l = 3, the subshell consists of seven f-orbitals.
• The boundary surface diagrams show that each f-orbital has three nodal surfaces and thus their shapes are
complex and difficult to represent by simple diagram.
g-orbital
THEORY OF BOND FORMATION
• Two theories which explain the bond formation are
1.Valence bond theory (VB Theory) by Linus Pauling

2.Molecular orbital theory (MO Theory) by Robert S. Mulliken Linus Pauling

Robert S. Mulliken
Valence Bond Theory (VB Theory)
• Valence bond theory explains the formation of covalent bonds in molecules
• It is based on the number of valence electrons and does not consider the other electrons in the atom.
• The VB theory is based on the concept of atomic orbital overlap.
• The VB theory uses the process of Hybridization.
• Atomic orbital overlap is the interaction of two atomic orbitals of two atoms followed by sharing of electrons
of atoms.
1. According to this theory covalent bonds are formed between atoms that are sufficiently closer and can overlap
their atomic orbitals.

2. Covalent bond is formed by a pair of electrons shared by two atoms.

3. Lone pair of electrons does not involve in bond formation.

Covalent bonding
Ionic bonding, Coordinate covalent bonding,
Coordinate bonding
Limitations of VB theory

1. This theory ignores the electrons other than the valence electrons.

2. It does not explain the partial ionic character of bonds.

3. It does not explain the bond formation in complex multi-atom molecules.

4. It cannot account for coordinate bond in which one atom donates both the electrons required for bond
formation.

5. It does not explain the bond formation in molecules like H2+ and He2+ which involves sharing of single
electron.
Linear Combination of Atomic Orbitals –
Molecular Orbitals (LCAO-MO)
• In the VB theory even after the formation of the molecule, the atomic orbitals
remain as such and retain their identity with respect to their atoms.

• In the MO theory, after the formation of the molecule, the valence electrons lose
their identity and they no longer belong to individual atoms but belong to molecule as a
whole.

MO theory VB theory
Salient features of Molecular Orbital theory

1. According to MO theory the atomic orbitals (AO) of the atoms combine to form new
orbitals known as molecular orbitals (MO).

2. Molecular orbitals are described by wave functions based on quantum chemistry.

3. Overlapping of two AO results in formation of two MO (i.e) one bonding MO and one
antibonding MO.
Wave function
• The wave function of the 1s orbital is always
1. Every atom can possess full set of s,p,d,f
positive sign (above the reference axis)
orbitals but not all of them will have electrons
• The wave function of 2p orbital is sometimes
2. The space where there is more probability of
positive sign (above the axis) and sometimes
finding electrons is called atomic orbital.
negative (below the axis). Thus changes sign
3. The representation of AO is called electron from positive to negative.
probability density diagram which show the
• The above fact is represented as electron
most probable distribution of electron cloud
probability density diagram (AO) with + or –
around the nuclei.
sign. These two sign indicates the relative
4. Each AO is described by a wave function. probabilities and – sign does not show that the
5. For example wave function of 1s and 2p orbital probability is negative.
is shown below where r is the distance • The probability density diagram describes the
between electron and nucleus. shape of the atomic orbital. Shapes of 1s orbital
and 2pz orbital are shown below.
Combination of wave function: Bonding and
Antibonding molecular orbitals
• Two waves can overlap in two different ways to form bonding molecular orbital or antibonding molecular
orbital.
• The overlap of the positive part of one AO with positive part of another AO and negative part of one AO with
negative part of another AO reinforces and produce a larger wave known as bonding molecular orbital.
• Similarly the overlap of the positive of one AO with the negative part of another AO results in destruction of
wave and produces an antibonding molecular orbital.
LCAO – MO of H2
• Molecular orbital is described by wave function similar to atomic orbital.
• The wave function of MO is obtained by Linear combination of atomic orbitals method.
• This concept can be explained by considering hydrogen molecule H2.
• Hydrogen molecule has two hydrogen atoms HA and HB whose atomic orbitals are described by wave
function φA and φB.
• These two atomic orbitals overlap (i.e) φA ± φB and produce a new wave function known as molecular
orbital. Such algebraic sum of functions is called as linear combination.

• The two normalized LCAO wave functions are

• WhereΨb and Ψa are wave function, Nband Na are Normalization constant of bonding and antibonding
molecular orbitals respectively. The numerical value of Nband Na was calculated to be 0.71 (~√½).
 Combination of s – s atomic orbitals to form bonding andantibonding molecular orbitals Combination of s–p atomic orbitals to form bonding and antibonding molecular orbitals

Combination of px–px atomic orbitals to form bonding andantibonding molecular orbitals Combination of py–pyatomic orbitals to form bonding andantibonding molecular orbitals
• The energy of LCAO-MO’s Ψb and Ψa is represented as Eb and Eaand is given as

• Where Ĥ is the Hamiltonian operator (total energy operator). Substituting the integrals with symbols

• Since both the atoms A and B are H atom, QA = QB = Q and the energy equation (4) becomes

• Similarly
• Here integral Q represents the energy of an electron in the orbital φA or φB that is equal to the
ground state energy of hydrogen atom.
• The integral β represents the energy of interaction between the orbitals φA and φB. It is called
exchange integral and is inherently negative.
• Thus an electron occupying bonding MO, Ψb is more stable and an electron in Ψa is less stable
than electron in a pure atomic orbital, φA or φB
• The actual energy of stabilization and destabilization is obtained by substituting Normalization
constant Na and Nb (Na = Nb = √½) in equation (8) and (9)
• Energy Level Diagram
• As the bonding and antibonding orbitals are formed, the AO
overlap, energy changes occur.
• The formation of the bonding MO (Ψb) decreases the energy and
that of antibonding MO (Ψa) increases the energy.
• The energy of the bonding MO is lower than that of antibonding
MO.
• The energy difference between AO and bonding MO is called
stabilization energy and it is denoted as β.
• The energy difference between AO and antibonding MO is
denoted as β.
• Each MO can accommodate two electrons with opposite spins
similar to AO.
• The energy of each electron is decreased by β and hence the total
reduction in energy of the system is 2β. This denotes the bond
energy.
• This reduction in energy is the driving force for bond formation.
• When two AO of H atoms combine, it forms lower energy bonding
MO which is designated as σ 1s and higher energy antibonding
MO which is designated as σ* 1s.
• The two electrons each from AO of H atom occupy the lower
energy bonding MO with opposite spins.
BAND THEORY
• Band theory is a quantum model which gives an insight about the possible energies of electrons in the solids
in order to understand the electrical and optical properties of solids.
• It is the molecular orbital theory extended to solids.
• A single atom has discrete energy states or energy levels of electrons,
• In the case of assembly of atoms (i.e., Solids), situation is different.
• When two atoms come closer, their atomic orbitals get overlapped to form new orbits called molecular
orbitals (bonding and antibonding).
• When large number of atoms are in close association as in case of solids, the discrete nature of energy levels
of atoms vanishes and there are formation of large number of energy levels having close energy differences
• This is called a band of energy levels or energy bands.
• This theory is explained by considering Lithium metal by adding Li atoms one by one to form Li2, Li3, Li4, and
so on till Lin

10m14an1
Salient Features of Band Theory
• When the atoms are brought together in solids, the atomic orbitals of the valence shells
‘interact’ forming molecular orbitals
• These energy levels with close energy difference forms the energy bands in which the
valence electrons are filled in the allowed energy levels
• The individual energies within an energy band are so-close together and considered to
be continuous
• A band is a group of infinitesimally energy levels in a solid/crystal
• The solids have three types of energy bands which are
• Valence band
• Forbidden band
• conduction band
• Valence band
• Valence band is the band of energy levels occupied by the
valence electrons.
• It is lowest in energy among three types of bands.
• It is generally fully filled in insulators, partially filled in
conductors by electrons and never empty Conduction
• Forbidden band Unfilled
Bands
band

• Electrons are absent in this energy band

• The energy band is between valence band and conduction
band
Band gap
• Electrons are either below it (which are bound to an atom-
Valence band) or above it (which are able to move freely- E

conduction band)
• This type of gap is known as band gap (Eg) Valence
Filled band
• Conduction band Bands

• The next permitted band, above the valence band, is called

the conduction band
• The electrons occupying this band are called conduction
electrons.
• It is higher in energy than the valence band and forbidden
band.
Energy bands in solids
• Electrons in this band have enough energy to move freely
and can gain energy from external electric field
Types of Solids based on band gap size and Energy
• Conductors
• Conductors have zero band gap energy.
• Valence band and conduction band are overlapped.
• Thus the electrons in the valence band can easily move into Overlap
conduction band without external energy.
• They are good conductors of electricity. Example: Metals
Conduction
• Insulators band
• Insulators have large band gap energy and band gap size.

Electron energy
------------------------
• It is difficult for an electron to jump from a valence band to Fermi level
Band
gap
conduction band.
• Absence of free electrons in the conduction band restricts
the flow of electric current in insulators.
Valence band
• Thus the insulators are poor conductors of electricity.
Example: Plastics
Metal
• Semiconductors Semi Conductor Insulator

• Semiconductors have small band gap energy and band gap

size.
• Thus with small amount of energy, the electron in valence
band can jump into conduction band
• Conductivity of semiconductors is between that of
insulators and conductors. Examples: Silicon, Germanium
etc
Types of Semiconductors
• Based on level of purity semiconductors are of two types
• Intrinsic semiconductors
• These are semiconductors are chemically pure and free from any
impurities. Examples: Si, Ge, etc
• This means no holes or vacancies in valence band are created by
impurities (external agent)
• They are also called undoped semiconductors
• The energy gap is so small (about 1 eV) thus when temperature is
increased electrons can jump from valence band to conduction
band.
• This increases the conductivity
• Extrinsic semiconductors Electron current
• These are basically intrinsic semiconductors whose conductivity can
be increased by addition of impurities called dopants
• Holes or electrons are created in valence band by dopants (external
agent)
• n-type dopants create electrons and p-type dopants create holes in
n-type and p-type semiconductors respectively
• Example: Arsenic in Silicon (n-type) and Gallium in Silicon (p-type)
Hole current
 Types of Extrinsic Semiconductor- Role of Arsenic and Gallium doping on Silicon
• Doping
• It is process of adding an impurity to the intrinsic
semiconductor to increase the electrical conductivity
• Dopant
• The impurity added to the semiconductor during
doping process is known as dopant
• n-type semiconductor
• n-type dopant such as As, P, Sb (pentavalent
element) added to Si
• Creates excess negatively charged electrons
• Loosely bound excess electrons jump from valence
band to conduction band when electric field is
applied
• Electrical conductivity – movement of excess
electrons in conduction band
• p-type semiconductor
• p-type dopant such as B, Ga,
Al (trivalent element) added
to Si
• Creates positively charged
holes
• Hole travels to adjacent atom
by acquiring an electron.
• Electrical conductivity –
Holes carry current by
accepting electrons and
move in opposite direction to
that of flow of electrons
10m16an1
 n-type semiconductor p-type semiconductor
• Addition of pentavalent impurity • Addition of trivalent impurity
like P or As or Sb to pure like B or Al or Ga to pure
intrinsic semiconductor form n- intrinsic semiconductor form p-
type semiconductor type semiconductor
• It contains excess negative • It contains excess positive
charged electrons due to charged holes due to impurity
impurity addition addition
• Example: As to Si • Example: Ga to Si
SUPERCONDUCTORS
• A superconductor is a material that can conduct electricity or
transport electrons from one atom to another with no resistance.
• This means no heat, sound or any other form of energy would be
released from the material when it has reached "critical
temperature" (Tc), or the temperature at which the material
becomes superconductive.
• Unfortunately, most materials must be in an extremely low energy
state (very cold) in order to become superconductive.
Heiki Kammerlingh Onnes
• Definition: Superconductors are materials which conduct
electricity without any electrical resistance or zero resistance. The
maximum temperature at which a superconducting material
exhibits superconductivity, is called its critical temperature (Tc).
• The phenomenon of superconductivity was first observed by Heiki
Kammerlingh Onnes, a Dutch physicist in 1913 and found that
mercury became superconducting at 4K (at boiling point of liquid
helium).
• Materials in superconducting state become diamagnetic and are
repelled by magnets.
 2.0

1.5

RT /R300K
1.0

Superconducting or zero electrical

resistivity at this temperature

0.5

100 200 300 400

Temperature (K)

Electrical resistivity on going to zero absolute in a

superconducting material
Meissner effect
• When a low magnetic field is applied to a superconductor and it is cooled to low
temperature below its transition temperature, then the superconductor expels all
magnetic flux. This is known as Meissner effect

The Meissner effect occurring when

a superconductor cooled by liquid
nitrogen levitates a magnet
Applications of superconductivity
1. Superconducting magnets capable of generating high fields with low power consumptions are being
employed in scientific tests and research equipments.

2. Superconducting magnets (niobium-titanium (NbTi) that becomes superconductive below 9.4°K) are also
used for magnetic resonance imaging (MRI) in the medical field as a diagnostic tool.

3. It is used as a magnet for high-energy particle accelerators.

4. It is used as a memory or storage elements in computers.

5. It is used in high-speed magnetically levigated trains.

6. It is used in high-speed switching and signal transmission for computers.

 Test your Understanding

• Elaborate the LCAO-MO method in the formation of hydrogen molecule

• Formulate the Schrodinger wave equation for a particle in one dimensional box and determine the wave
function and energy of the particle
• Explain the various shapes of atomic orbitals with neat sketch
• Explain band theory of solids with neat diagram
• Explain the role of doping of arsenic and gallium on silicon with neat diagram
• Summarize the significance of four quantum numbers
Test your Understanding
• Tell de Broglie’s hypothesis
• Define Heisenberg’s Uncertainty principle
• What are the conditions for acceptable wave functions?
• Define zero point energy for 1D box
• What happens to spacing of energy levels when length of one dimensional box increases?
• What is probability density?
• List out the types of quantum numbers
• Define atomic orbital
• Write the radial and angular wavefunction of 1s orbital of hydrogen atom or (write the complete wavefunction of 1s
orbital of hydrogen atom)
• Draw the structure of p-orbitals
• Classify solids based on energy band gap.
• Differentiate between n-type and p-type semiconductor
• What are super conductors? Give example
• Define Meissner effect
• List out the applications of superconductors
• Calculate the zero point energy of an electron of mass 9.1 x 10-31Kg in one dimensional box of length 1Å
• Calculate the energy difference between E3 and E2 for an electron in a one dimensional box of length 12Å
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