Inorganic Chemistry (CY11001)

Chemical Bonding: Part-I

Introduction, Planck equation, Photoelectric Effect, de Broglie eqn,
Heisenberg uncertainty principle, Schrӧdinger Equation
Books to Refer:
Inorganic Chemistry by Shriver & Atkins
Inorganic Chemistry by James E. Huheey
Physical Chemistry: Atkins
Fundamental Concepts of Inorganic Chemistry A. K. Das
Prof. Partha Pratim Jana
Department of Chemistry
Organic Building(2nd Floor)
Ph: 03222-283330
Email: ppj@chem.iitkgp.ac.in
 Origin of the Quantum Mechanics
Newton’s corpuscular theory of light (1675)

Wave theory by Thomas Young, Hygen, Maxwell

Last two decades of 19th century, a number of experimental observation reported
do not have any explanation from classical theory.

a) energy distribution in black body radiation

b) photoelectric effect

c) variation of heat capacity of solid with temperature

d) atomic spectral lines, etc.

Max Planck (1900) introduced the concept of Quantum Theory

 Planck’s Quantum Theory

The radiation can only be absorbed or emitted in quanta

of energy, hν.
E = Energy of photon
ν = Frequency of emitted radiation
h = Planck constant
Proposed his quantum theory and explains the results of
black body radiation by a assuming that a black body
radiates energy discontinuously in discrete energy packets
called quanta and given by the equation above.
 The Photoelectic Effect
When UV light is incident on a metal plate (alkali or alkaline earth metal) in a vacuum, it
emits electrons.

Characteristics:
i) Photoelectric current (I) ∞ the intensity
of the incident beam of certain ν .
ii) ν≥ threshold frequency (νo).
iii) Emax dependent of ν (indepandent of
intensity) and metal plate.

Classical electromagnetic theory of light can’t explain

 The Photoelectic Effect
Potential of the A is –ve w.r.t. C
Potential of the A is +ve w.r.t.C

Stopping potential: The minimum required retarding potential to stop the photoelectric
current is called the stopping potential (Vs).
KEmax=(½)mu2=eVs
Saturation current: A certain positive value of the potential , there will be no further
increase of current. This is called saturation current.
 Einstein’Theory of Photoelectic Effect
•Classical electromagnetic theory of light fails to explain (Characteristics: ii & iii)
•Explained the phenomenon by quantum theory of radiations.
•Proves this the particle nature of light.

• hν is the energy of the incident light.

• Light can be thought of as a bunch of particles which
have energy E = hν (Max Planck). The light particles
are called photons.
 Einstein’Theory of Photoelectric Effect
All or none principle: When a photon strikes an electron , either the whole energy of
the photon or no energy of the photon will be transferred to the electron.
Energy will be utilised in three successive steps:
•bringing the target electron to the surface from the binding forces within the metal
• releasing the electron from the surface,
•Imparting the kinetic energy (K.E.) to the released electron.
K.E. of surface electron> K.E. of bulk electron
Work funcion (ω) of a metal: The minimum amount of energy to overcome the
binding forces within a metal to release electron. It is expressed in term of
threshold frequency (νo), ω= hνo

• KEmax = ½(mu2) = hν- ω

• eVs = h(ν- νo)
This is Einstein’s equation.
when the total energy of photon is used in ejecting the electrons it is simply said that the
photon is absorbed.
 Conclusion

i) ν<νo, no photoelectric emission regardless of intensity

ii) Maximum Kinetic Energy and consequently stopping potential (Vs) are independent
of intensity of incident photon but linearly dependent with the frequency of incident
photon. This aspect is verified by Millikan.

• Vs = (hν/e)- (h νo/e)
Vs
tanθ=h/e
θ From the slope, h can be obtained from
h νo/e ν the known value of charge of the electron.

Millikan determined the value of Planck constant in this method and it was in
good agreement with the result obtained from other sources.
This verification validate the Einstein’s equation.
-34
h=6.631x10 J. sec
 Work Function (ω) and Ionisation potential (IP)

The electrons at the outermost shell of the atom residing at the surface for a particular
metal are having minimum binding energy. For the same type of electrons within the bulk,
binding energy is higher.
Both the process deal with minimum amount of energy to knock out the most loosely bound
electron, in case of photoelectric effect the metal is in solid state , while in case of ionisation
potential, metal atom is in gaseous and isolated condition.

Metal λo (nm) ω (eV) IP1 (eV)

threshold
Na 500 2.50 5.12
K 550 2.26 4.32
Cs 660 1.87 3.88
Cu 290 4.30 7.70
Ag 261 4.73 7.54
Zn 359 3.44 9.37

Magnitude of ω is always lower compared to its corresponding IP1.

 De Broglie wavelength for matter wave
Wave Particle Duality

• E = mc2
Einstein’s law of mass energy equivalence
• E = hν
Planck Equation
• mc2 = hν
(1892-1987)
p=mc = h/λ { since ν = c/λ}
De Broglie extended this idea to all the other particles travelling with a
finite velocity.
Wavelength of a particle of mass m moving with the velocity u is given
by
λ = h/mc = h/p
p = momentum of electron
The wave is called matter wave
λ = de Broglie wavelength
 The de Broglie Wavelength
Macroscopic and Microscopic Bodies

Q1 An electron in hydrogen atom to move with a velocity , u=2.3x10-6 ms-1. Calculate the
value of wavelength (λ)? me=9.1x10-31 kg.

λ =3.16 Å ( comparable to X-ray and it is measurable as well as believable)

Q2 A marble ball of mass 1g to move with velocity, u=2 ms-1. Calculate the corresponding
λ?
λ= 3.312 x10-29 cm
E=6x105 J.
λ is associated with a tremendously high energy wave which is unbelievable in our sense.

De Broglie wave equation has no significance for the macroscopic particle.

 Bohr Quantum restriction from de Broglie
Concept
Quantum restriction required to define stationary orbit does not find any support
from classical theory.
According to the Bohr theory stationary orbit is defined by the relation,
mur = nh/2Π
The revolving electron in a particular stationary orbit considered as
stationary wave.
Stationary wave: Position of its maxima and minima do not change with
time.
 Werner Heisenberg

1887-1961
• It is impossible to specify the exact position and velocity (momentum) of a
subatomic particle simultaneously.
• Uncertainty Principle.
• ∆x ∆p ≥ h/4π where h is Plank’s Constant, a fundamental constant with
the value 6.626×10-34 J s.
 Application of Uncertainty Principle
In case of large particles
A ball of mass 2 g whose uncertainly in position is equal to 10-8 cm. Calculate the
corresponding uncertainly in the velocity?

Trajectories of moving particles can be determine very precisely.

In case of small particles,

Let us consider fate of electron in a hydrogen atom. Mass of electron 9.1x10-31 kg. Let
us consider that the position of the electron from the nucleus can be determined with
an uncertainly of 4 pm (4x10-12 m). For instance, electron in the Bohr’s first orbit
having r in the range 43±4 pm. Calculate the uncertainty in the velocity of the
electron?

Expected velocity of the electron from Bohr’s theory is found to be 2.2 x106 ms-1.

The Bohr’s orbit become meaningless in the light of uncertainly principle.

Probability concept of the electron cloud.

 Summary
Flaws of classical mechanics

Photoelectric effect

Heisenberg uncertainty principle limits

simultaneous knowledge of conjugate variables

Light and matter exhibit wave-particle duality

Relation between wave and particle properties

given by the de Broglie relations

The state of a system in classical mechanics is defined by

specifying all the forces acting and all the position and
velocity of the particles.
 Schrӧdinger Wave Equation
(1926)

• It is required to have the concept of probable distribution patter of the

electron cloud rather than well defined trajectory.
• Mathematical concept of wave –particle dualism to the electron in an atom
by considering the electron as standing wave as in the vibrating sting fixed
at both the ends by Schrӧdinger
• Development of wave mechanics to tackle the problems in both atomic and
molecular physics
• It is the differential equation of 2nd order

The equation w.r.to space for a stationary wave can be

∂2 Ψ /∂x2 + ∂2 Ψ /∂y2 + ∂2 Ψ /∂z2 + (8π2m/h2)( E-V) Ψ = 0

Ψ -Amplitude of the matter associated with the particle at various points defined
by x,y,z space coordinates w.r.t . a certain reference frame.
 Representation of Schrӧdinger Wave Equation
The equation for a standing sine wave in a vibrating sting fixed at two ends

Ψ -Amplitude of the wave varing sinusoidally along x.

The classical wave equation for the standing wave

Total energy
E=T+V
Kinetic energy of a moving particle
2
T=P /2m
From the de Broglie relation, we get

Schrodinger’s wave equation with respect to space for a particle moving in one direction,
 (∂2 Ψ /∂x2 + ∂2 Ψ /∂y2 + ∂2 Ψ /∂z2) + (8π2m/h2)( E-V) Ψ = 0

{(-h2/8π2m)(∂2/∂x2 + ∂2/∂y2 + ∂2/∂z2) + V} Ψ = E Ψ

2
∇ Laplacian operator

• {(− h2/8π2m) ∇2 + V}ψ = Εψ

 Hψ = Εψ
• Η = {(− h2/8π2m)∇2 + V} Hamiltonian Operator
• When operator H on ψ it gives the E

∇2ψ + (8π2m/ h2)(E - V) ψ = 0

 Physical Significance of Schrӧdinger Wave Equation
The equation gets developed by incorporating non-classical be Brolie’s equation into
the classical wave equation.
(-h2/8π2m)(∂2/∂x2 + ∂2/∂y2 + ∂2/∂z2) Ψ + V (x,y,z) Ψ = E Ψ

Significance of operator K

Corresponding to classical Ekin there is an operator in wave mechanics

K= (1/2m)(-ħ2∂2/∂x2 -ħ2 ∂2/∂y2 -ħ2∂2/∂z2)= -(ħ2/2m)∇2

(px)2= -ħ2∂2/∂x2= i2ħ2∂2/∂x2= (-iħ∂/∂x)2= (-iħ∂/∂x) (-iħ∂/∂x)
px =(-iħ∂/∂x) and px*=(iħ∂/∂x)

Schrӧdinger Wave Equation is a wave mechanical analogue to the classical eqn. of energy
 Eigen values and Eigen Function

i. Ψ must be continuous
ii. Ψ Must be finite
iii. Ψ Must be single valued at a particular point , there can not be more than one
vaule of for Ψ.
iv. The first order derivatives of Ψ w. r. to its variables (∂/∂x, ∂/∂y, ∂/∂z) must
be continuous w.r.to x, y, z respectively. There must not be any sudden change in Ψ
when its variables are changed.
v. The probability of finding the particle over the whole space must be unity.
∫ Ψ2 dτ=1 (small volume element given by dx. dy.dz)
vi. For the bound states, Ψ must vanish at infinity and in case of complex wave
function Ψ Ψ* vanishes at infinity.

The solutions, i.e. wave functions, which satisfy the above conditions are
called eigen functions and the energies corresponding to eigen functions are
called eigen values.
 Physical Significance of the wave function (Ψ)

The sign of the wave function has not direct physical significance:
the positive and negative regions of this wave function both
corresponds to the same probability distribution. Positive and
negative regions of the wave function may corresponds to a high
probability of finding a particle in a region.
 Characteristics of Wave Function

In general ψ ψ* is to be considered for interpretation.

In Classical mechanics, square of wave amplitude at any point

associated with any electromagnetic radiation is a measure of
radiation intensity at that point.
In a similar way, ψ2 or ψ ψ* may be related to density or appropriately
the probability of finding the electron in the space.
The wave function Ψ is the probability amplitude

ψ = ψ *ψ
2

Probability density
• ∫Ψ2 dτ = 1 Normalized wave function
• If Ψ is complex then replace Ψ2 by ΨΨ*

• If the function is not normalized, it can be done

by multiplication of the wave function by a
constant N such that N2Ψ2 gives the actual
probability in the volume element dτ.
• N2 ∫Ψ2 dτ = 1
• N is termed as Normalization Constant
• ∫Ψ2 dτ = 1 Normalized wave function
• If Ψ is complex then replace Ψ2 by ΨΨ*

• If the function is not normalized, it can be done

by multiplication of the wave function by a
constant N such that

• N2 ∫Ψ2 dτ = 1
• N is termed as Normalization constant
Q. A free particle of energy mass m is allowed to move freely without
any restriction in a field. Find out the energy values (E) and wave
function of the particle.
 How to write Hamiltonian for different
systems?
{(-h2/8π2m)∇2 + V} Ψ = E Ψ
-e
• Hydrogen atom:
2 2
r
• KE = ½ m (vx + vy + vz2)
• PE = -e2/r (in CGS system), or PE = -e2/4πε0r ( in SI system)
• r = distance between the electron and the nucleus) +Ze
• H = {(-h2/8π2m) ∇2 –e2/r}
• ∇2 Ψ + (8π2 m/h2)(E+e2/r) Ψ = 0
• If the effective nuclear charge is Ze
• H = {(-h2/8π2m )∇2 –Ze2/r}
 +
H2 Molecule
e (x,y,z)

ra rb

A RAB B

the wave function depends on the coordinates of the two nuclei,

represented by RA and RB, and of the single electron, represented by r1.
 +
e (x,y,z)
H2
{(-h2/8π2m)∇2 + V} Ψ = E Ψ ra
rb
A Rab B

• PE = V = -e2/ra – e2/rb + e2/Rab V = -e2 [1/ra+1/rb-1/Rab]

• H = (-h2/8π2m)∇2 + ( – e2/ra - e2/rb + e2/Rab)

• The Wave equation is
• ∇2 Ψ + (8π2 m/h2) (E+ e2/ra + e2/rb – e2/Rab) Ψ = 0
Born-Oppenheimer approximation
 e1 (x1, y1, z1)
He Atom
r12
r1

e2 (x2, y2, z2) r2 Nucleus (+2e)

{(-h2/8π2m)∇2 + V} Ψ = E Ψ
• V = -2e2/r1 – 2e2/r2 + e2/r12
• H = (-h2/8π2m) (∇12 + ∇22) + V
• The Wave equation is
• (∇12 + ∇22 )Ψ + (8π2 m/h2)(E-V) Ψ = 0
 e1 (x1, y1, z1) r12 e2 (x2, y2, z2)
ra2
H2 r
a1 rb2
rb1
A Ra B
b
• PE = V = ?
• H = (-h2/8π2m)(∇12 + ∇22) + V
• The Wave equation is
• (∇12 + ∇22 )Ψ + (8π2 m/h2)(E-V) Ψ = 0
 V = -e2[1/ra1+1/rb1 + 1/ra2 +1/rb2 -1/r12 -1/Rab]

attractive potential energy Electron-electron repulsion

Internuclear repulsion
 Chemical Bonding
• Two existing theories,
• Molecular Orbital Theory (MOT)
• Valence Bond Theory (VBT)
Molecular Orbital Theory
• MOT starts with the idea that the quantum
mechanical principles applied to atoms
may be applied equally well to the
molecules.
 Linear combination of atomic orbitals

Rules for linear combination (EOS)

1. Atomic orbitals must be roughly of the same energy.

2. The orbital must overlap one another as much as

possible- atoms must be close enough for effective
overlap.
3. In order to produce bonding and antibonding MOs,
either the symmetry of two atomic orbital must remain
unchanged when rotated about the internuclear line or
both atomic orbitals must change symmetry in identical
manner.
 Rules for the use of MOs
* When two AOs mix, two MOs will be produced

* Pauli principle

* Aufbau principle

* Hund’s rule

Bond order = ½ (bonding electrons – antibonding

electrons)
 Linear Combination of Atomic Orbitals (LCAO)

The wave function for the molecular orbitals can be

approximated by taking linear combinations of atomic
orbitals.

A B
ψA ψB

ψAB = N(cA ψA + cBψB) c – extent to which each AO

contributes to the MO
ψ2AB = (cA2 ψA2 + 2cAcB ψA ψB + cB2 ψB 2)

Probability density Overlap integral

 Energy level diagram
EA - β
β
ψA ψB
β

EA + β
Eigen functions (ψ): No physical significance
ψ2 : bears a meaningful significance 2
∫Ψ dτ = 1
Schrӧdinger Equation in polar coordinates (Atkins)
Solutions to ψ: Born Oppenheimer Principle
Variation Theorem (Atkins)
 Constructive interference

. + .
+. +.
ψg bonding
cA = cB = 1

ψg = N [ψA + ψB]
Amplitudes of wave
functions added
 node

+. -. +. .-
cA = +1, cB = -1 ψu
antibonding
ψu = N [ψA - ψB]

Destructive interference
Nodal plane perpendicular to the
H-H bond axis (en density = 0)
Energy of the en in this orbital is
higher.
ΨA-ΨB

Amplitudes of wave
functions
subtracted.
 H2

11.4 eV
LCAO of n A.O ⇒ n M.O.
109 nm

Location of
Bonding orbital
4.5 eV
 The overlap integral

The extent to which two atomic orbitals on different atom

overlaps : the overlap integral

S = ∫ ψ A ψ B dτ
*
 S > 0 Bonding S < 0 anti

Bond strength depends on the

S = 0 nonbonding
degree of overlap
 Homonuclear Diatomics
• MOs may be classified according to:
(i) Their symmetry around the molecular axis.
(ii) Their bonding and antibonding character.
• σ1s< σ1s*< σ2s< σ2s*< σ2p< πy(2p) = πz(2p)
<πy*(2p) =πz*(2p)<σ2p*.
 dx2-dy2 and dxy

2-
Cl4Re ReCl4
 g- identical B
under inversion
A
u- not identical
Place labels g or u in this diagram

σ∗u

π∗g

πu

σg
 First period diatomic molecules
H H2 H σ1s2

σu*
Bond order: 1
Energy

1s 1s

σg

Bond order =
½ (bonding electrons – antibonding electrons)
 Diatomic molecules: The bonding in He2

He He2 He
σ1s2, σ*1s2

σu*
Bond order: 0
Energy

1s 1s

σg

Molecular Orbital theory is powerful because it allows us to predict whether

molecules should exist or not and it gives us a clear picture of the
electronic structure of any hypothetical molecule that we can imagine.
Why He2 does not exist, but He2* exist!
Second period diatomic molecules

Li Li2 Li σ1s2, σ*1s2, σ2s2

2σu* Bond order: 1

2s 2s
Energy

2σg

1σu*

1s 1s
1σg
Diatomic molecules: Homonuclear Molecules of the Second Period

Be Be2 Be

2σu*

2s 2s σ1s2, σ*1s2, σ2s2, σ*2s2

Energy

2σg
Bond order: 0

1σu*

1s 1s
1σg
Simplified
Simplified
MO diagram for B2

3σu*
1πg*

1πu
3σg
Diamagnetic??
Contradicts the theoretical
Prediction from simple
Molecular orbital diagram
2σu*

2σg
Same symmetry, energy mix-the one with higher energy moves higher
and the one with lower energy moves lower
 MO diagram for B2
B B2 B

3σu*
3σu*
1πg*

1πg*

2p (px,py)
1πu
3σg 2p
LUMO 3σg

2σu* HOMO 1πu

2σu*

2s 2s

2σg
2σg

X
Diamagnetic Paramagnetic
C2
3σ g*

1πu*
2p
3σ g
1πu

3σ g

2σ u *
2s

2σg

X
Paramagnetic ? Diamagnetic
N2
Bond lengths in diatomic molecules

Filling bonding orbitals

Filling antibonding
orbitals
NO+ is readily stabilised in many compounds such as NO+HSO4- -Explain