INTRODUCTION TO

CHEMICAL BONDING

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Failure of Classical Mechanics
• Total energy, E = ½ mv2 + V(x)
• p = mv (p = momentum)
• E = p2/2m + V(x) ………..Eq.1

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• Newton’s second law, which is a relation
between the acceleration d2x/dt2 of a
particle and the force F(x) it experiences.
• Therefore, v = p/m
• Or, dp/dt = F(x),
• Continuous variation of energy is
possible.

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• Certain experiments done in late 19th
century and early in this century gave
results, totally at variance with the
predictions of classical physics. All
however, could be explained on the basis
that, classical physics is wrong in allowing
systems to possess arbitrary amounts of
energy. For example, photoelectric effect.
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A young Max Planck was to give a lecture on radiant heat. When he

arrived he inquired as to the room number for the Planck lecture. He

was told, "You are much too young to be attending the lecture of the

esteemed professor Planck."

• Max Planck E = hν

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Photoelectric Effect.

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 Major objections to the
Rutherford-Bohr model
• We are able to define the
position and velocity of each
electron precisely.
• In principle we can follow the
motion of each individual
electron precisely like planet.
• Neither is valid.
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• It is impossible to specify the exact
position and momentum of a 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. 10
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Einstein could never accept some of the revolutionary
ideas of quantum mechanics ("God does not play
dice"). When reminded in 1927 that he revolutionized
science 20 years earlier, Einstein replied, "A good joke
should not be repeated too often."

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Einstein

KE 1/2mv2 = hν- φ
• φ is the work function
• hν is the energy of the incident light.
• Light can be thought of as a bunch of
particles which have energy E = hν. The
light particles are called photons.
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If light can behave as particles,why
not particles behave as wave?

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 Louis de Broglie

• Particles can behave as wave.

• Relation between wavelength λ and the
mass and velocity of the particles.
• E = hν and also E = mc2,
• E is the energy
• m is the mass of the particle
• c is the velocity.
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• E = mc2 = hν
• mc2 = hν
• p = h /λ { since ν = c/λ}
• λ = h/p = h/mv
• This is known as wave particle duality

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 Wave equation?
Schrödinger Equation.
• Energy Levels
• Most significant feature of the Quantum
Mechanics: Limits the energies to discrete
values.
• Quantization.

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 Classical Equation: Electromagnetic Radiation:

u = Amplitude

Separate Variables

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Introduce standard wave equation solution for f(t)

We can write eiωt d2ψ/dx2 = (1/v2) d2(eiωt)/dt2 ψ(x)

eiωt d2ψ/dx2 = (-ω2/v2)(eiωt) ψ(x)

Total Energy

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 Solution

From de Broglie Equation

ω2/v2 in terms of λ

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 Therefore form

Schroedinger Equation in One Dimension

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 Schroedinger Equation in Three dimension

If ψ is a function of (x, y, z) then we can write the equation as

Or

Hψ = Eψ

·H = - ħ2/2m ∇2 + V; Hamiltonian operator

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 How to write Hamiltonian for
different systems?
• Hydrogen atom:
• KE = ½ m (vx2 + vy2 + vz2)
• PE = -e2/r, (r = distance between the
electron and the nucleus.)
• 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} 23
 H2+ molecule

e (x,y,z)

ra rb

A(+e) RAB B(+e)

PE = V = -e2/ra – e2/rb + e2/Rab

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

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• Characteristics of Wave Function
Born has been described as
a moody and impulsive person.
He would tell his student,
"You must not mind my being
rude. I have a resistance
against accepting something
new. I get angry and swear
but always accept after a
time if it is right."

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 Characteristics of Wave
Function
• Heisenberg’s Uncertainty principle: We
can never know exactly where the
particle is.
• Let ρ (x, y, z) be the probability function,
• ∫ρ dτ = 1
• Our knowledge of the position of a
particle can never be absolute.
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Connection with Wave Function

• Let Ψ (x, y, z) be the solution of the wave

equation for the wave function. Then we
may anticipate that
• ρ (x, y, z) ∝ Ψ2 (x, y, z)
• Choosing a constant in such a way that
the ∝ is converted to =
• ρ (x, y, z) = Ψ2 (x, y, z)
• ∴∫Ψ2 dτ = 1
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• Normalized wave function.
• If the function is not:
• 1/N2 = ∫Ψ2(x, y, z) dτ

• If Ψ is complex then Ψ2 is replaced by ΨΨ*.

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 Unacceptable and Acceptable wave
functions:
• Acceptable:
• .For electron bound to an atom/molecule,
the wave function must be every where
finite.
• .Single valued.
• .Continuous.
• .Gradient (dΨ/dt) must be finite
• .∫Ψ2 dτ is finite, so that Ψ can be
normalized.
• Stationary States
• E = Eigen Value ;Ψ is Eigen Function 30
 One Dimensional Box
• V=∝ a V=∝

• V V

•x=0 x=a
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 The Wave Eqn. is
• d2Ψ/dx2 + 8π2m/h2[EΨ] = 0
• d2Ψ/dx2 + k2Ψ = 0
• k2 = {8π2m/h2}}E]
• Solution is
• Ψ = C cos kx + D sin kx
• Applying Boundary conditions:
• Ψ = 0 at x = 0 ⇒ C = 0
• Ψ = 0 at x = a

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• Ψ = 0 at x = a
• D sin ka = 0
• sin ka = 0 or ka = nπ
• n = 0, 1, 2, 3, 4…….
• Ψn = D sin (nπ/a)x
• k2 = {8π2m/h2}[E] or E = k2h2/ 8π2m
• E = n2 h2/ 8ma2
• n = 0 not acceptable: Ψn = 0
• Lowest kinetic Energy = E0 = h2/8ma2
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 Need for Effective Approximate Method of
Solving the Wave Equation.
• Born Oppenheimer Principle.
The Born-Oppenheimer Approximation is the assumption that the electronic motion
and the nuclear motion in molecules can be separated. It leads to a molecular wave
function in terms of electron positions ri and nuclear positions Rj.

•The electronic wave function depends upon the nuclear positions Rj but not
upon their velocities, i.e., the nuclear motion is so much slower than electron
motion that they can be considered to be fixed.
•The nuclear motion (e.g., rotation, vibration) sees a smeared out potential
from the speedy electrons.
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• How can we get the most suitable approximate wave

function?

• How can we use this approximate wave function to

calculate energy E?

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 Variation Method

• HΨ = EΨ

• Ψ HΨ = Ψ EΨ = EΨ Ψ

• E = ∫ΨH Ψ dτ/∫Ψ2 dτ

• If Ψ is complex, E = ∫ Ψ*H Ψ dτ/ ∫ Ψ* Ψdτ

• <Ψ/H/ Ψ> /<Ψ/ Ψ> ……4

• Bra-Ket notation 36
• E can be calculated. If the wave function is not known,

we can either make an educated guess or use Variation

Theorem.

• The nature of the equation 4 suggest that even if Ψ is not

correct, we should consider a quantity E with dimension

of energy, which is related to Ψ by

• E = <Ψ/H/ Ψ> /<Ψ/ Ψ>

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• Ψ1 ⇒ E1
• Ψ2⇒ E2
• The Variation Theorem tells that
• E1 , E2> Eg, Eg ground state energy
• E1 > E2
• E2 and Ψ2 is the better approximation.

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• We can chose a whole family of wave function at the

same time, like trial function with one or more variable

parameters C1, C2, C3,….

• Then E is function of C1, C2, C3 …….etc. C1, C2, C3 …. Etc.

are such that E is minimized with respect to them.

• We will utilize this method in explaining chemical

bonding.
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 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 molecule
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 We can write the following principles
• Each electron in a molecule is described by a
certain wave function Ψ - Molecular Orbital
(MO).

• Each Ψ is defined by certain quantum numbers,

which govern its energy and its shape.

• Each Ψ is associated with a definite energy value.

• Each electron has a spin, ± ½ and labeled by its

spin quantum number ms.

• When building the molecule- Aufbau Principle

(Building Principle) - Pauli Exclusion Principle. 42
Simplest possible molecule - H+2 two nuclei
and a single electron.

• Let the two nuclei be labeled as A and B.

ΨA and ΨB: Wave functions
• Since the complete MO has
characteristics separately possessed by
ΨA and ΨB,
• Ψ = CA Ψ A + CB Ψ B
• or Ψ = N(ΨA +λ ΨB)
• λ = CA/CB, and N - normalization
constant. 43
 This method is known as Linear
Combination of Atomic Orbitals or LCAO.

• ΨA and ΨB are same atomic orbitals except for

their different origin.

• By symmetry ΨA and ΨB must appear with

equal weight and we can therefore write

• λ2 = 1, or λ = ±1

• Therefore, the two allowed MO’s are

• Ψ = Ψ A± Ψ B 44
 For ΨA+ ΨB we can now
calculate the energy
• From Variation Theorem we can write the
energy function as

• E = <ΨA+ΨB/H/ΨA+ΨB>/<ΨA+ΨB/ ΨA+ΨB>

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Let us take the nominator of the right
hand side of the above equation:

• <ΨA+ΨB/H/ΨA+ΨB> = <ΨA/H/ ΨA> +

• <ΨB/H/ ΨB> +
• <ΨA/H/ ΨB> +
• <ΨB/H/ ΨA>
• = <ΨA/H/ ΨA> + <ΨB/H/ ΨB> +2<ΨA/H/
Ψ B>
• Now <ΨA/H/ ΨA> or <ΨB/H/ ΨB> is the
ground state energy of a hydrogen atom 46
Now <ΨA/H/ ΨA> or <ΨB/H/ ΨB> is the ground state energy of
a hydrogen atom

• let us call this as EA

• <ΨA/H/ ΨB> = <ΨB/H/ ΨA> = β =
resonance integral.

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 The denominator:
• <ΨA+ΨB/ ΨA+ΨB> = <ΨA/ΨA> +
• <ΨB/ΨB> +
• <ΨA/ΨB> +
• <ΨB/ΨA>
• = <ΨA/ΨA> + <ΨB/ΨB> + 2<ΨA/ΨB>
• <ΨA/ΨB> = <ΨB/ΨA> = S, Overlap
integral. Also we know that ΨA and ΨB
are separately normalized, so <ΨA/ΨA> =
<ΨB/ΨB> = 1
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• E =[2EA + 2β] / 2(1 + S)
• Or E+ = [EA + β]/ (1 + S)
• Similarly, E- = [EA - β]/ (1 – S)
• Numerically S is very small, so if we neglect
S, we can write
• E± = EA ± β

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 Energy level diagram

EA - β

ΨB --------------------------- ΨB

EA + β

Figure 5

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 Homonuclear Diatomics
• MOs may be classified according to-
(i)Their symmetry around the molecular
axis
• (ii)Their bonding and antibonding
character.
• (iii) The atomic orbitals into which they
separate at large internuclear distances.
• σ1s<σ1s*<σ2s<σ2s*<σ2p<πy(2p) =
πz(2p)<πy*(2p)=πz*(2p)<σ2p*.
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 In drawing this diagram we
have ignored one fact.
• We have assumed that there is no
interaction between 2s and 2p orbitals.
• This is not true.
• Thus from Li to at least N there is strong
interaction between the 2s and 2p
orbitals.

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Bond enthalpy increases as bond order increases.

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Bond length decreases as bond order increases.

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 Heteronuclear Diatomics

• In the case of heteronuclear diatomic molecules whatever

arguments are presented above are valid.

• The only difference is that the energy level diagram is not

symmetrical.

• The bonding MOs are closer to the atomic orbitals which

are lower in energy

• The antibonding MOs are closer to those higher in energy

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