Unit-1
STRUCTURE AND BONDING MODELS
The arrangements of various types of electromagnetic radiations in terms of increasing or
decreasing wavelengths or frequency is called an electromagnetic spectrum. The spectrum
obtained by white light is a continuous spectrum. For example, the visible light is the form of
electromagnetic radiation that lies in the wavelength range of 3800—7600 Å. The wavelengths
of various waves increase in the following order (Fig).
γ-rays < X-rays < UV rays < Visible rays < IR rays <Microwaves < Radio waves
Planck Quantum theory
In 1900, Max Planck proposed a theory of radiation to explain these
phenomena. While analyzing the light emitted by heated objects, he
discovered that the emitted light is non-continuous and is in the form
of defined energy packets. These small packets of energy are known
as quanta or photons. The energy of the photon is directly proportional
to the frequency of the radiation.
Mathematically,
ε = hυ
where 'ε' energy of the photon
υ = frequency of the radiation
h= Planck's constant
Planck Quantum theory
Further, the total energy emitted or absorbed by a body is
always in integer and multiple of 'hυ', i.e.,
ε = nhυ
where n = l, 2, 3, ..
For example, hυ, 2 hυ, 3 hυ, 4 hυbut never a fraction.
Similarly
ε = (⸫υ =)
Louis de Broglie
Born : 15 August 1892
Died : 19 March 1987 (aged 94)
Education: University of Paris
Awards: Nobel Prize in Physics (1929)
De Broglie's hypothesis
According to de Broglie's hypothesis, all the matter particles
like electrons, protons, neutrons, atoms should have not only
the particle nature but also the wave properties. The
wavelength of the matter particle (electron) in motion is
given by
λ = or λ =
where λ= wavelength
m= mass of the
electron
h= Planck's constant
P = movement of
De Broglie's Derivation
According to Max Planck's Quantum theory
ε = hυ
= (⸫υ =) (1)
According to Einstein mass energy relation
E = mc2
Comparing the two equations
= mc2
λ=
If c' is replaced with the velocity of electrons 'υ', then
λ = or λ =
de-Broglie's concept is significant for small (microscopic) particles like electrons only. For macroscopic
particle, the wavelength is so short and wave properties cannot be observed. Thus, as per this theory,
an electron is not a point mass moving in an orbit but a standing wave extending around the nucleus in
a circular fashion (Fig. 1.3).
Werner Heisenberg
Born : 5 December 1901
Died : 1 February 1976 (aged
74)
Awards: Nobel Prize (1932)
Heisenberg Uncertainty principle
The Heisenberg Uncertainty principle states that 'It is impossible to
determine simultaneously both the position and momentum of a
microscopic particle like an electron with accuracy'.
Mathematically, the relation is
Δx.Δp≥
Δx.mΔv≥
Where Δx =uncertainty in position
Δp= uncertainty in momentum, i.e., mΔv
m= mass of electron
If the position of the particle is known exactly (Δx= 0), then Δυ becomes
infinity and vice versa.
Heisenberg Uncertainty principle
Case. I.
If the position 0f the particle known exactly (Δx= O),
then
Δx. Δυ =
Δυ =
Δυ =
=∞
Heisenberg Uncertainty principle
Case. 2. If the velocity of the particle is known exactly (Δυ = O), then
Δx. Δυ =
Δx =
Δx =
=∞
The uncertainty principle has no significance for macromolecules. The
uncertainty principle which gives the wave nature of the electron only
provides the probability of finding the electron in a given space. Therefore,
the classical concept of Bohr's model of the atom has been replaced by
probabilities approach.
Schrodinger wave equation
A standing wave having wavelength (λ) that has an
amplitude at any point along x direction is
mathematically described as a function f(x)
=−
Schrodinger wave equation
If a wave function f(x) is represented as 𝝍 (psi) the
equation can be written as
=−ψ … ….(2)
Schrodinger wave equation
When this standing wave is considered in 3 dimensions
having x, y and z coordinates
+ + =−ψ …. …(4)
Schrodinger wave equation
∇2ψ =−ψ
∇2ψ = + +
𝛁 is called Del Operator
Schrodinger wave equation
de Broglie states that
λ=
λ2 =
Schrodinger wave equation
∇2ψ =−ψ
∇2ψ + ψ =0 ….(6)
Schrodinger wave equation
The total energy (E) of system is
given as
𝑬 = 𝑲. 𝑬. + 𝑽
K. E.= E-V
=𝑬–𝑽
Schrodinger wave equation
= 2m(E-V)
ψ + ψ =0 ……(7)
Particle in a Box
As shown in Fig. 1.5, a particle of mass 'm', which is
free to move along x-direction between x z: O and x d
is inside a box bounded by infinity rigid walls. As per
the quantum mechanics, the potential energy (V) of the
particle infinite on both sides of the box and inside the
box V is constant (V O). CP function has to be zero at x
0 and all negative values of x, since the particle is not
allowed over the walls of the box. Similarly, V function
must be zero for all values x d. Therefore, it can be
stated that the particle is combined with the box and
cannot exist outside the box.
Particle in a Box
Inside the box, the Schrodinger's wave equation is
+m (E−V)ψ =0
+m (Eψ) =0 since V =0 ….(5)
Particle in a Box
Ψ must be zero outside the region x = 0 and x= d, so that ψ
must be continuous
in the region between x= 0 and x =d. A general solution of
Schrodinger's equation is
ψ = a sin b cos
Particle in a Box
where a =Maximum amplitude of ψ and b =constant.
In order to satisfy the condition of ψ=0 at x=0, the second
term, i.e.,
b cos should be zero.
Particle in a Box
At the other boundary conditions ψ = 0 at at x=d, then
Ψ = a sin (2mE)1/2d=0
= sin (2mE)1/2d=0
= (2mE)1/2d= nπ
On squaring and rearranging of above equations, we get (7)
Particle in a Box
En =
where n= l, 2, 3, 4, ……∞
Thus, a particle in a box does not possess any arbitrary
amount of energy, rather it possesses a discrete set of
energy values, i.e., its energy is quantized.
Particle in a Box
Some of the energy levels are
E1 =
E2 =
E3 =
Therefore, according to the above equation, a particle in a
box (bound particle) possess quantized energy but a free
particle does not.
Wave function: ψ(x)
ψ is a wave function and refers to the amplitude of electron
wave i.e. probability amplitude. It has got no physical
significance. The wave function ψ may be positive, negative or
imaginary.
Probability density: ψ2
ψ2 is known as and determines the probability of finding
an electron at a point within the atom. This means that
if:
ψ2is zero, the probability of finding an electron at that
point is negligible.
ψ2 is high, the probability of finding an electron is high
i.e. electron is present at that place for a long time.
ψ2 is low. the probability of finding an electron is low i.e.
electron is present at that place for a shorter time.
Atomic and Molecular Orbitals Molecular Orbital (MO)
The wave function of an electron in an The wave function of an electron in a
atom is called atomic orbitals molecule is called molecular orbital
Atomic orbitals is mono centric Molecular orbital is polycentric
No bonding and anti-bonding atomic There are bonding anti-bonding
orbitals molecular orbitals.
It is less stable. It is more stable.
It has a simple It has a complex shape.
Atomic orbitals are designated as Molecular orbitals designated as
s, p, d, f etc., , *, , *, , *
Bonding Molecular Orbitals Anti-bonding Molecular Orbitals
The bonding molecular orbital is formed by a Anti-bonding molecular orbital is formed by a
linear combination of two atomic orbitals when linear combination Of two atomic orbitals when
their wave functions are added their wave functions are subtracted.
It has lower energy and greater stability It has higher energy and lower stability compared
compared to that of the combining atomic to that of the combining atomic orbitals.
orbitals.
Probability of finding the electrons within the The probability of finding the electrons within the
inter-nuclear region is greater than that of the inter-nuclear region decreases and becomes zero.
overlapping atomic orbitals.
It has no nodal plane It has a nodal plane.
(plane where the electron density is zero).
The energy difference between the bonding The energy difference between the anti-bonding
molecular orbital and the combining atomic molecular orbital and the combining atomic
orbitals is as stabilization energy orbitals is known as de-stabilization energy.
The linear combination of atomic orbitals with the The linear Combination of atomic orbitals with
same sign on their lobes takes place. opposite signs on their lobes takes place.
Designated by , , etc. Designated by *, *, * etc.
Salient Features of Molecular
Orbital Theory
1. n (AO + AO) = n(MO)
2. AO + AO = BMO
3. AO-AO = ABMO
4. E of BMO < E of AO
5. E of ABMO > E of AO
Salient Features of Molecular
Orbital Theory
Its follows Aufbau principle
electrons fill lower-energy atomic
orbitals before filling higher-energy ones
Salient Features of Molecular
Orbital Theory
Its follows HUNDS-RULE
every orbital in a subshell is singly occupied with one electron before any
one orbital is doubly occupied, and all electrons in singly occupied orbitals
have the same spin.
Salient Features of Molecular
Orbital Theory
Its follows Pauli exclusion principle
no two electrons in the same atom can have
identical values for all four of their quantum
numbers
S-S Orbital combination
S-P Orbital combination
P-P Orbital combination
LCAO METHOD
LCAO METHOD
Case l. When two waves are in phase
constructive interference occurs, the waves are added so that the wave function of
the new wave, i.e., bonding molecular orbital (Ψb) is
Ψb= ΨA+ ΨB
Case 2. When the two waves are out of phase,
destructive interference occurs, the waves are subtracted from each other so that the
wave function of the new wave, i.e., anti-bonding molecular orbital (Ψa) is
Ψa= ΨA- ΨB
LCAO METHOD
Ψ2b= (ΨA+ ΨB)2
Ψ2b= Ψ2A+ Ψ2B+2ΨAΨB
i.e., Ψ2b> Ψ2A+ Ψ2B
Ψ2a= (ΨA-ΨB)2
Ψ2a= Ψ2A+ Ψ2B-2ΨAΨB
i.e., Ψ2a< Ψ2A+ Ψ2B
Molecular orbital energy-level diagram for B2 molecule
Molecular orbital energy-level diagram for N2 molecule
Molecular orbital energy-level diagram for C2 molecule
Molecular orbital energy-level diagram for O2 molecule
Molecular orbital energy-level diagram for NO molecule
Pi molecular orbitals of Butadiene
•Butadiene is a conjugated diene consisting of two adjacent pi-bonds and
comprised of 4 p-orbitals and 4 pi-electrons.
•To draw the molecular orbital diagram of butadiene, start by drawing 4 p-
orbitals all aligned with the same phase. This has zero nodes and is
the lowest energy pi-orbital (π1 )
•As the number of nodes in an orbital increases, so does its energy. The
highest-energy molecular orbital has three nodes and has all p-orbitals
with opposite phases (π4)
Pi molecular orbitals of Butadiene
•Intermediate orbitals (π2 ) and (π3 ) have one and two nodes,
respectively.
•Once the molecular orbital diagram is built, the next step is to add
the 4 pi-electrons. This will fill up the lowest-energy orbital (π1 )
and the second-lowest-energy orbital (π2 )
•The highest-occupied molecular orbital (HOMO) of butadiene is
the highest-energy orbital that contains pi-electrons. This is π2
•The lowest-unoccupied molecular orbital (LUMO) of butadiene is
the lowest-energy orbital that has zero pi-electrons. This is π3
Pi molecular orbitals of Butadiene
Pi molecular orbitals of Benzene
A molecular orbital description of benzene provides a more satisfying
and more general treatment of "aromaticity". We know that benzene has
a planar hexagonal structure in which all the carbon atoms are
sp2 hybridized, and all the carbon-carbon bonds are equal in length. As
shown below, the remaining cyclic array of six p-orbitals ( one on each
carbon) overlap to generate six molecular orbitals, three bonding and
three antibonding. The plus and minus signs shown in the diagram do
not represent electrostatic charge, but refer to phase signs in the
equations that describe these orbitals (in the diagram the phases are also
color coded).
Pi molecular orbitals of Benzene
When the phases correspond, the orbitals overlap to generate a
common region of like phase, with those orbitals having the
greatest overlap (e.g. π1) being lowest in energy. The remaining
carbon valence electrons then occupy these molecular orbitals in
pairs, resulting in a fully occupied (6 electrons) set of bonding
molecular orbitals. It is this completely filled set of bonding
orbitals, or closed shell, that gives the benzene ring its
thermodynamic and chemical stability, just as a filled valence
shell octet confers stability on the inert gases.
Pi molecular orbitals of Benzene
Bethe and Vanvleck proposed Crystal Field Theory (CET)
which was later extended by Orgel.
Shape of d-orbitals
Salient features of CFT
This theory is mainly applicable to transition metals. According to this
theory, the central metal ion of the complex is regarded as a point
charge.
Similarly, surrounding ligands are considered as point masses.
Bonding between the central metal ion and the surrounding ligands
are assumed to be ionic
i.e., bonding between a central metal ion and its ligands simply arises
from the purely electrostatic force of attraction (an attraction
between a positively charged metal ion and negative charge of the
ligand or partial negative charge of ligand).
Salient features CFT
If the ligand is a neutral molecule, the negative end of the dipole is
attracted towards the central positive metal ion.
The five d-orbitals (dxy, dyz, dzx, dX2-y2 and dz2) in a metal atom or ion have the
same energy (degenerate orbitals). This degeneracy is maintained if a
spherically symmetrical field of negative charges surrounds the metal atom
or ion.
If the negative filed is due to ligands in a complex, it becomes
asymmetrical and the degeneracy of the orbitals is changed and results in
the splitting of the d-orbitals. The pattern of splitting depends upon the
nature of the crystal field.
CFT- Octahedral complex
In the octahedral complex, six ligands occupy the six corners of an octahedron.
There will be repulsion between the electrons in metal d-orbitals and the electrons
of the ligands.
However, not all the d-electrons will be affected equally.
CFT- Octahedral complex
Those in the dX2-y2 and dz2and orbitals (eg orbitals) which are directed along
the x, y and z axes will be repelled more than those in the dxy, dyz and dzx
orbitals (t2g orbitals) which are directed between these axes.
Hence, under the influence of the approaching ligands, the electrons in the
orbitals dX2-y2 and dz2 and exist in the higher energy levels compared to dxy, dyz
and dzx.
This splitting of the degenerate levels due to the presence of a definite
geometry is known as Crystal Field Splitting.
CFT- Octahedral complex
CFT- Octahedral complex
The difference between the eg and t2g orbitals is designated by
∆o (subscript 'o' denotes an octahedral environment) or 10Dq.
This is called crystal field stabilization energy (CFSE). The two
eg orbitals are raised by 3/5 ∆o or 0.6 ∆o or 6Dq and three
orbitals are lowered by 2/5 ∆o or 0.4 ∆o or 4Dq. in octahedral
field.
CFT- Tetrahedral complex
In a tetrahedral complex, the splitting is the reverse of
octahedral splitting. The direction of approach of the four
ligands does not coincide exactly with the eg or t2g
orbitals.
Now, the approach of ligands raises the energy for both
eg and t2g sets of orbitals. However, the energy of t2g sets
of orbitals is raised maximum, since they are closest to
the ligands.
Therefore, crystal splitting is opposite of that takes place
in octahedral complexes.
CFT- Tetrahedral complex
CFT- Tetrahedral complex
For the same metal, same ligands and metal-ligand
distance, the relation between tetrahedral splitting energy
(∆t) and octahedral splitting energy (∆o) is
∆t = 2/3 x 2/3 = 4/9 ∆o
Thus, the tetrahedral splitting (∆t) is always much smaller than the
octahedral splitting (∆o). The splitting of the d-orbitals is given in Fig.
in a tetrahedral field.
CFT- Tetrahedral complex
