Module – I

Molecular structure and Band theory of Solids

Imaginary structure of an atom

Introductions:
Atom: The building blocks of matter are atoms.
A smallest indivisible particle of an element/matter/substance is called atom. In an atom,
subatomic particles like protons and neutrons are present inside the nucleus and negatively
charged electrons are present outside the nucleus.
Orbit: A fixed path in which electrons revolve around the nucleus of an atom is called orbit.
Orbital: A region having the highest probability of finding electrons (outside the nucleus) in an
orbit called orbital.
Atomic orbital:
 The region just outside the nucleus, where the probability of finding electrons is at the
highest (95%) is orbital.
 Atomic orbitals are also called as energy levels, designated as s, p, d and f orbitals.
 Each orbital has a unique energy associated with it, can contain a maximum of two
electrons and varies in shape and spatial orientation.
 Each orbital in an atom is characterized by a unique set of values of the three quantum
numbers n, ℓ, and m, which respectively correspond to the electron's energy, angular
momentum, and magnetic quantum number.
 Each such orbital can be occupied by a maximum of two electrons, each with its own spin
quantum number s.
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  The simple names s-orbital, p-orbital, d-orbital and f-orbital refer to orbitals with angular
momentum quantum number ℓ = 0, 1, 2 and 3 respectively.
 Atomic orbitals are labelled as s, p, d and f orbitals. All four orbitals have different shapes.
 The energies of orbitals are in order of s<p<d<f
s-orbital:
 It is spherical in shape. The shape of the orbital depends on the quantum number associated with
an energy state.
 Nodal Plane: The plane passing through the nucleus on which the probability of finding electrons
is zero, is called as nodal plane
 No of nodal plane in an orbital = Azimuthal quantum number (l).
 In the case of s-orbital nodal plane is zero.
 These are also called as angular nodes. It is non-directional. s-Orbital has only one sub energy
level

S-orbital
p-orbitals:
 p-orbital is classified in to three types.
 p- Orbital has three sub-energy levels (Px, Py and Pz).
 The shape of the p-orbital is dumbbell shape.
 In the case of px orbital the electron is located along x-axis and we can’t find any electrons in y
and z-axis.
 In the case of py orbital the electron is located along y-axis and we can’t find any electrons in x
and z-axis.
 In the case of pz orbital the electron is located along z-axis and we can’t find any electrons in x
and y-axis.
 p-orbital is directional. Each p-orbital contains lobes which lie on either side of the plane passing
through the nucleus.
 Number of nodal plans is Px Py and Pz is 1.

P-orbitals

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d-orbitals: d-Orbital has five sub-energy levels, i.e., dxy, dyz, dzx, dx2-y2 and dz2.
 The shape of the d-orbital is double dumbbell.
 d-orbital is directional.
 Number of Nodal Planes = 2.
 These d-orbital are classified into five types.
 t2g and eg are two categories of d-orbital. Triply degenerate orbital t2g (dxy, dyz, dzx), doubly
degenerate orbital eg (dx2-y2), dz2.

t2g Type: In this types lobes or electrons are located in between the axis.
Lobes represent the presence of the electron.

dxy dyz dzx

Nodal plane = 2 Nodal plane = 2 Nodal plane = 2

eg Type: In this type the lobes or electrons are present along the axis. i.e., the electrons are present
along the axis in case of eg type in d-orbitals. (dx2-y2), and dz2 are the part of eg type.

dz2 orbital has 3D structure i.e., dumb-bell in xz plane and spherical in yx-plane makes the number of
nodal plane to be zero. Though there exists some region where probability of finding electron is zero but
no full nodal plane exists.
f-orbitals:
There is maximum space of seven orbitals and 14 electrons.
The seven f-orbitals are: fx3, fy3, fz3, fx(y2-z2), fy (x2-z2) and fz(x2-y2), fxyz.
There is no discrete shape in the f-subshell. This is because of the complexity of its name.

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QUANTUM NUMBERS
Position and energy of electrons is completely described by four sets of quantum numbers.
1. Principal quantum number (n):
Principal quantum number was proposed by Neils Bohr and denoted by “n”.
It tells about the distance from the nucleus (or size of orbit) and energy of electron.
n = Integer with positive value
If, n = 1, i.e., 1st orbit; n = 2, i.e., 2nd orbit; n = 3, i.e., 3rd orbit; n = 4, i.e., 4th orbit.
Total no of electrons presents in a shell = 2n2
2. Azimuthal or Angular quantum number (l):
Azimuthal or Angular quantum number was proposed by Sommerfeld and it is denoted by ‘l’.
It describes the shape of orbitals (s, p, d and f).
Value of l is from 0 to (n-1).
l = 0 for s-orbital, l = 1 for p-orbital, l = 2 for d-orbital, l = 3 for f-orbital.
3. Magnetic quantum number (m or ml):
Magnetic quantum number was proposed by Lande and indicated by ‘m or m l’.
It describes about the number of orbitals and orientation of subshell.
Magnetic quantum number values are (2l+1) and they are from –l····0 ··· +l (including zero).
If, l = 0, then m = 1, i.e., 0
l = 1, then m = 3, i.e., -1, 0, +1
l = 2, then m = 5, i.e., -2, -1, 0, +1, +2
l = 3, then m = 7, i.e., -3, -2, -1, 0, +1, +2, +3
4. Spin quantum numbers (s or ms):
Spin quantum number was proposed by Beck (George Uhlenbeck)) and Goudsmit (Samuel
Goudsmit) and denoted by ms.
It describes the spin of electrons. Spin quantum numbers are only two, those are +1/2 and 1/2.
Clockwise direction 1 Anticlockwise direction 1
↑ + ↓
2 2

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 FILLING OF ATOMIC ORBITALS WITH ELECTRONS
1. Aufbau principle: Aufbau principle states that the electrons are filled into atomic orbitals from
lowest energy orbital to highest energy orbitals.
Example, carbon has 6 electrons. Electronic configuration is 1S2 2S2 2P2.
2. Hund’s rule: All degenerate orbitals in a subshell occupy with one electron before any orbital
occupy with two electrons, and all electrons in singly occupied orbitals have same spin.
Example: 3d: ↑ ↑ ↑ ↑ ↑
3. Pauli Exclusion Principle: Pauli Exclusion Principle states that, any two electrons do not have
four same quantum numbers in an atom.
Examples: Hydrogen ↑ Helium ↑↓ Lithium ↑↓ ↑
1S1 1S2 1S2 2S1

Molecule: Two or more atoms connected through chemical bonds is called molecule.
Molecular orbitals: A mathematical function describing the location and wave-like behavior of
an electron in a molecule called molecular orbital.
Shapes of Molecular Orbitals
Molecular orbitals are two types, σ-molecular orbitals and π-molecular orbitals. σ-Molecular
orbitals are formed when two atomic orbitals overlap along the internuclear axis. π-Molecular
orbitals are formed when two atomic orbitals overlap in sideways.
1. Molecular orbitals from s-atomic orbitals (s-s overlap)
s-Atomic orbitals can overlap only through internuclear axis. Therefore, s-atomic orbitals produce
only σ-molecular orbitals and cannot give π-molecular orbitals. Molecular orbitals which are
formed through addition method are called as bonding molecular orbitals (BMO). Molecular
orbitals which are formed through subtraction method are called as antibonding molecular
orbitals (ABMO).

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 (electron density between
nucleus is low)

(electron density between

nucleus is high)

2. Molecular orbitals from 2p-atomic orbitals (p-p overlap)

p-Atomic orbitals can overlap through internuclear axis as well as in sideways. Therefore, p
atomic orbitals can produce both σ and π-type molecular orbitals. When p-atomic orbitals
overlap through internuclear axis produce σ-molecular orbitals, and when p-atomic orbitals
overlap through sideways produce π-molecular orbitals. The strongest overlap occurs between
the 2pz orbitals

.
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 MOLECULAR ORBITAL THEORY (MOT)
Molecular orbital theory (MOT) was developed by F. Hund and R. S. Mulliken. MOT clearly
describes the structure and properties of different molecules.
The important postulates of MOT are as follows

 MO theory was originally called the Hund-Mulliken theory.

 Atomic orbitals of comparable energy and proper symmetry combine together to form
molecular orbitals.
 The movement of electrons in a molecular orbital is influenced by all the nuclei of
combining atoms. (Molecular orbital is poly centric in nature).
 The number of molecular orbitals formed is equal to the number of combining atomic
orbitals.
 When two atomic orbitals (AO's) combine together two molecular orbitals (MO's) are
formed.
 Molecular orbitals are of two types
a) Bonding MO
b) Anti-bonding MO.
 One molecular orbital possess higher energy than corresponding atomic orbitals and is called anti
bonding molecular orbital (ABMO) ABMOs are formed through subtraction method. and the
other has lower energy and is called bonding molecular orbitals (BMO) BMOs are formed
through addition method..
 In molecules electrons are present in molecular orbitals. The electron filling is in
accordance with Pauli's exclusion principle, Aufbau principle and Hund's rule. Resonance
has no role in MOT.
 MOT explains magnetic properties, colour of transition elements etc. The anti-bonding
molecular orbital is less stable and has higher energy than the corresponding bonding
orbitals.
 Degenerate molecular orbitals have similar energies.
 Sigma molecular orbital is more stable compared to pi molecular orbital.
 Bond order (BO) = [𝑵𝒃 − 𝑵𝒂]/𝟐. Where, Nb is number of electrons present in BMO, and Na

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 is number of electrons present in ABMO.
 Bond order (BO) is a measure of the strength of the bond between two atoms.
 Higher the BO, higher is the dissociation energy.
 Bond length is inversely proportional to bond order.
 A positive value of BO reveals that the molecule exists and is stable.

 When BO is zero, the molecule is unstable and it does not exist.

 A molecule is paramagnetic in nature, if it contains one or more unpaired electrons in its

molecular orbitals. But if the molecule does not have any unpaired electrons, it will be
diamagnetic in nature.

Characteristics of bonding molecular orbitals :

1. The probability of finding the electron in the internuclear region of the bonding
molecularorbital is greater than that of combining atomic orbitals.
2. The electrons present in the bonding molecular orbital result in the attraction between thetwo
atoms.
3. As a result of attraction, the bonding molecular orbital has lower energy and hence greater
stability than that of the combining atomic orbitals.
4. They are formed by the additive effect of the atomic orbitals i.e. crest fall over the crestand
troughs over the trough so that the amplitude of the new wave is given by Φ= ΨA + ΨB
5. They are represented by σ, π, and δ.
Characteristics of antibonding mcular orbitals :
1. The probability of finding the electron in the inter nuclear region decreases in the antibonding
molecular orbitals.
2. The electrons present in the antibonding molecular orbital result in the repulsion between the
two atoms.
3. Because of the repulsive force, the antibonding molecular orbitals has higher energy and lower
stability i.e. it does not favour the formation of bond.
4. They are formed by the subtractive effect of the atomic orbitals i.e. crests falls over the troughs
so that the amplitude of the new wave is given by Φ= ΨA - ΨB

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5. They are represented by σ* , π* , δ*

Difference between Bonding and Antibonding Molecular Orbitals :

Bonding Molecular Orbitals Anti-Bonding Molecular Orbitals

Molecular orbitals formed by the additive effect of
the atomic orbitals is called bonding molecular
orbitals
Probability of finding the electrons is more in
thecase of bonding molecular orbitals
These are formed by the combination of + and + and
– with – part of the electron waves
The electron density, in the bonding molecular
orbital in the inter nuclear region, is high. As a
result, the nuclei are shielded from each other and
hence the repulsion is very less.
The bonding molecular orbitals are represented
byσ, π, δ.
Molecular orbitals formed by the subtractive effect
ofatomic is called anti-bonding molecular orbitals
Probability of finding electrons is less in antibonding
molecular orbitals. There is also a node between
the anti-bonding molecular orbital between two
nuclei where the electron density is zero.
These are formed by the overlap of + with – part.
The electron density in the anti bonding molecular
orbital in the inter nuclear region is very low and so
the nuclei are directly exposed to each other.
Therefore the nuclei are less shielded from each
other.
The corresponding anti-bonding molecular orbitals
represented by σ*, π*, δ*.

LINEAR COMBINATION OF ATOMIC ORBITALS (LCAO)

Atomic orbitals can be expressed by wave functions (ψ) which represents the amplitude of
electron waves, but it may not be easy to solve for molecules.
To overcome this problem researcher developed an approximate method to obtain wave
functions for molecular orbitals known as linear combination of atomic orbitals (LCAO) method.
Consider the hydrogen molecule (H2) consisting of two hydrogen atoms HA and HB. Each
hydrogenatom in the ground state has one electron in 1s orbital, then the overall wave function
of H2 molecule is as follows. Here, orbitals are represented by wave function (ψ).
ψM.O = ψA ± ψB

ψBMO = ψA + ψB and ψABMO = ψA – ψB

A molecular orbital formed by addition of atomic orbitals is called bonding molecular orbitals
(BMO).
Indeed, the probability of finding electron is in square form,
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 i.e., ψ2BMO = (ψA + ψB)2 and ψ2 = (ψA – ψB)2
ABMO
ψ2BMO = ψ2A + ψ2B + 2 ψAψB and ψ2ABMO = ψ2A + ψ2B – 2 ψAψB

A molecular orbital formed by subtraction of atomic orbitals is called antibonding molecular

orbitals (ABMO).
MOLECUALR ORBITAL ENERGY LEVEL DIAGRAN (MOED) OF VARIOUS DIASTOMIC MOLECULES

A molecular orbital energy-level diagram shows the relative energies of the atomic orbitals of
atoms and the bonding, anti-bonding molecular orbitals they form.

Energy of all the molecular orbitals increases in the following order.

If number of electrons < 14
σ1s<σ*1s<σ2s<σ*2s<π2py=π2pz<σ2px <π*2py = π*2pz < σ*2px
If number of electrons > 14
σ1s<σ*1s<σ2s<σ*2s<σ2px<π2py=π2pz< π*2py = π*2pz < σ*2px

The molecular orbital and energy level diagram of F2

Atomic number of fluorine (F) is 9. No of electrons in fluorine atom (F) = 9. No of electronsin

fluorine molecule (F2) = 18.
 Electronic configuration of fluorine atom is 1s2 2s2 2p5.

 The electronic configuration of N2 is: σ 1s2<σ*1s2<σ2s2<σ*2s2<σ2px2<π2py2=π2pz2< π*2py2 = π*2pz2

< σ*2px0

 Bond order =

Where, Nb = no of bonding electrons & Na = no of anti-bonding electrons.

Then, BO = (10-8)/2 = 1
In F2 molecule BO is one means a single bond is present between two florin atoms.
 F2 does not have any unpaired electrons, so, F2 has diamagnetic property.
 F2 molecule doesn’t have unpaired electrons, so, F2 has diamagnetic property.




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

σ*2px

ABMO

π*2py= π*2pz
2px 2py 2pz 2pz 2py 2px
π2py= π2pz BMO

σ2px
σ*2s
Energy

2S 2S
σ2s
σ*1s

1S 1S
Atomic Orbitals σ1s Atomic Orbitals
of F-Atom of F-Atom
Molecular Orbitals
of F2-Molecule

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The molecular orbital and energy level diagram of Cl2

 Atomic number of chlorine (Cl) is 17. No of electrons in chlorine atom (N) = 17. No of
electronsin nitrogen molecule (N2) = 34.
 Electronic configuration of chlorine atom is 1s2 2s2 2p63s23p5.

 The electronic configuration of Cl2 is: σ3s2<σ*3s2<σ3px2<π3py2=π3pz2< π*3py2 = π*3pz2 < σ*2px0

 Bond order =

Where, Nb = no of bonding electrons & Na = no of anti-bonding electrons.

Then, BO = (8-6)/2 = 1
In F2 molecule BO is one means a single bond is present between two florin atoms.
 Cl2 does not have any unpaired electrons, so, Cl2 has diamagnetic property.

σ*3px

ABMO

π*3py= π*3pz
3px 3py 3pz 3pz 3py 3px
π3py= π3pz BMO

σ3px
σ*3s
Energy

3S 3S
σ3s
Atomic Orbitals
of Cl-Atom Atomic Orbitals
of Cl-tom
Molecular Orbitals
of Cl2-Molecule

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 The molecular orbital and energy level diagram of CO.

σ*2pz

ABMO
π*2px= π*2py

2px 2py 2pz

σ2pz 2pz 2py 2px

BMO

π2px= π2py
Energy

σ*2s

2S
σ2s 2S

σ*1s

1S
σ1s 1S
Atomic Orbitals Atomic Orbitals
of C-Atom of O-Atom
Molecular Orbitals
of CO-Molecule

 Atomic number of carbon (C) is 6. No of electrons in carbon atom (C) = 6. Electronic configuration of
carbon atom is 1s2 2s2 2p2.
 Atomic number of Oxygen (O) is 8. No of electrons in Oxygen atom (O) = 8. Electronic
configuration of carbon atom is 1s2 2s2 2p4.
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  No of electronsin Carbon mono-oxide (CO) = 14.
 The electronic configuration of CO is: σ 1s2<σ*1s2<σ2s2<σ*2s2 <π2py2=π2pz2<σ2px2< π*2py0 = π*2pz0
< σ*2px0

 Bond order =

Where, Nb = no of bonding electrons & Na = no of anti-bonding electrons.

Then, BO = (10-4)/2 = 3
In CO molecule BO is three means a triple bond is present between two carbon and oxygen atoms.
 CO does not have any unpaired electrons, so, CO has diamagnetic property.

The molecular orbital and energy level diagram of NO.

 Atomic number of Nitrogen (N) is 7. No of electrons in Nitrogen atom (N) = 7. Electronic
configuration of nitrogen atom is 1s2 2s2 2p3.
 Atomic number of Oxygen (O) is 8. No of electrons in Oxygen atom (O) = 8. . Electronic
configuration of carbon atom is 1s2 2s2 2p4.

 No of electrons in Nitrogen monoxide (NO) = 15.

 The electronic configuration of CO is: σ 1s2<σ*1s2<σ2s2<σ*2s2 <π2py2=π2pz2<σ2px2< π*2py1
= π*2pz0 < σ*2px0

 Bond order =

Where, Nb = no of bonding electrons & Na = no of anti-bonding electrons.

Then, BO = (10-5)/2 = 2.5
In NO molecule BO is 2.5 means bond is intermediate to a triple bond and double.

 NO is having one unpaired electron so NO is paramagnetic nature.

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 σ*2pz

ABMO
π*2px= π*2py

2px 2py 2pz

π2px= π2py 2pz 2py 2px

BMO

σ2pz
Energy

σ*2s

2S
σ2s 2S

σ*1s

1S
σ1s 1S
Atomic Orbitals Atomic Orbitals
of N-Atom of O-Atom
Molecular Orbitals
of NO-Molecule

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MOLECULAR ORBITALS OF 1,3-BUTADIENE
 s 1 3- s 2 CH=CH2
Node: The probability of finding electron is zero called as node.
 1,3butadiene contains two double bonds that are in conjugation. It is built from 4 sp2
hybridized carbon atoms, each contributing one p-atomic orbital containing one electron.
 From valence orbital theory we might expect that the C2-C3 bond is a sigma bond, would be able
to rotate freely.
 However, it is observed that there is a barrier to rotation about the C2-C3 bond.
 In addition, the C2-C3 bond is 148 pm, shorter than a typical carbon-carbon single bond (154
pm), longer than a typical double bond (134 pm).
 Molecular orbital theory accounts for these observations with the concept of delocalized pi
bonds.

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  The number of molecular orbitals for π-system is equal to the number of contributing
p-orbitals.

 Since butadiene consists of 4 individual p-orbitals, butadiene will contain 4 π-molecular

orbitals.

 The number of nodes between p-orbitals increases by one for each successive energy
level,such that the highest energy orbital has (n-1) nodes.

 The lowest energy orbital that is π1 molecular orbital always has zero nodes between
the p-atomic orbitals. π1 has three bonding interactions between C1-C2, C2-C3 and C3-C4.
π1 has zero antibonding interactions.
 π2 molecular orbital has one nodal plane between C2-C3. π2 has
3
two bonding
interactions between C1-C2 and C3-C4 but one antibonding interaction between C2-C3.
*
 π3* molecular orbital has two nodal planes between C1-C2 and C3-C4. π has one
bonding interactions between C2-C3 but two antibonding interactions between C1-C2
and C3-C4.
 π4* molecular orbital has three nodal planes between C1-C2, C2-C3 and C3-C4. π4* has
no bonding interactions but three antibonding interactions between C1-C2, C2 –C3 and
C3-C4.
 The highest occupied molecular orbital (HOMO) is π2 in 1,3-butadiene.In contrast, the
anti-bonding π3* orbitals contain no electrons. The lowest unoccupied orbital (LUMO) is
π3* in 1,3-butadiene.

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 π-MOLECULAR ORBITALS OF BENZENE AND AROMATICITY

No of B.I. = 0
3 No of anti B.I. = 6

n
o
d
e
s

No of B.I. = 2 Benzene
No of anti B.I. = 4 No of B.I. = 0
No of anti B.I. = 4
2 nodes LUMO
Energy

1 nodes HOMO
No of B.I. = 2
No of B.I. = 4 No of anti B.I. = 2
No of anti B.I. = 2

No of B.I. = 6
0 node No of anti B.I. = 0

HOMO : Highest Occupied Molecular Orbital & LUMO : Lowest Unoccupied Molecular Orbital
B. I. = Bonding Interactions & anti B.I. = anti bonding interactions

 Benzene (C6H6) is the simplest aromatic hydrocarbon. Benzene has a planar

hexagonal structure. All the carbon atoms are sp2 hybridized, each contributing p-
atomic orbitals containing one electron.
 Since benzene consists of 6 individual p-orbitals, the π-system of benzene will
contain 6-π molecular orbitals.
 The molecular orbitals of benzene: π1, π2 and π3 are bonding molecular orbitals (BMO).
π 4*, π5* and π6* are antibonding molecular orbitals (ABMO).

 The lowest-energy orbital (π1) always has zero nodes between the p-atomic
orbitals. π1 has six bonding interactions and zero antibonding interactions.
 π2 and π3 are degenerate orbitals (means same energy orbitals) and have one
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 nodal plane. π2 has four bonding interactions and two antibonding interactions.
π3 has two bonding interactions and two antibonding interactions.

 π4* and π5* are degenerate orbitals and have two nodal planes. π4* has two
bonding interactions and four antibonding interactions. π5* has zero bonding
interactions and four antibonding interactions.

 π6* has three nodal planes. π6* has zero bonding interactions and six antibonding
interactions.
 Benzene has 6π electrons which are filled in π1, π2 and π3 molecular orbitals.
 The HOMO is π2 and π3 in benzene & the LUMO is π 4*and π5* in benzene. 

Crystal Field Theory


This theory was proposed by Bethe & vanVleck
Postulates:
 According to this theory the bond between the metal ion and ligand consider as
ionic bond.
 In between the metal ion and ligand electrostatic force of attraction arise which
leads to formations of ionic bond.
 According to this theory the – vely charged ligands called as point charges (like Cl-
, Br-,OX2-)and neutral ligands called as point dipoles (H2O,NH3 ect).
 In free metal atom or ion all the d-orbitals (dxy, dyz, dzx, dx2-y2 and dz2) are lesser
energetic (stable) and in degenerate level.
 When metal atom or ion is placed in ligand solution all the ligand surround the
metal atom in a spherically symmetric way the degeneracy of d-orbitals are lifted
(energy reses) based on some ligands come very close to the metal then in
between the Me-s & L e-s repulsions arises as results the degeneracy of d-
orbitals destroyed .
 Some d-orbital energy decrease (lower energy orbitals), and some other d-orbital
energy increase (higher energy d-orbitas) this type of splitting is known as d-
orbital splitting or crystal field splitting.
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  This splitting depends on approaching way of ligands
 The energy difference between lower energy & higher energy orbitals is called as
crystal field splitting energy (Δ).
 Compare to free metal number of unpaired electrons becomes less in complex
then it is called as low spin complex & compared to free metal number of
unpaired electrons remains same in complex it is known as high spin complex.
 The electron excitation from lower energy d-orbital to higher energy d-orbital is
known as d-d transition for this transition required energy absorbed from visible
region radiation as a results complex exhibits colour.
 Orientation of d-orbitals
 d-orbitals oriented in between the X, Y, Z axis these are called as triple
degenerated orbital & represented as t2g, orbitals .
 d-orbitals oriented along the X, Y, Z axis these are called as double degenerated
orbital & represented as eg orbitals .

Spectrochemical series:
I- < Br- < S2- < SCN - < Cl- < F- < OH- < C2O4 2-
< H2O < NCS- < EDTA4- < pyridine < NH3 <
ethylene diamine < o-dipyridyl < 1,10-phenanthroline < NO2- < CN- < CO.
From I- to H2O are week field ligands
From NCS- to CO are strong field ligands.
 It is possible to list ligands or metal ions in order of increasing field strength in a
“spectro chemical series “.
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  Weak field ligands induce less splitting of the crystal fields. They form complexes
with high spins. Examples: chloride ions, fluoride ions etc.
 Strong field ligands result in greater splitting of the crystal field. They form
complexes with low spins. Examples: Co and cyanide ion.
 In the presence of weak field ligands splitting less electrons are not getting paired
resulting in a paramagnetic complexes.
 In the presence of strong field ligands splitting more electrons are getting paired
resulting in dia magnetic complexes.
Crystal field splitting in Octahedral Complexes
In octahedral complexes six ligands occupy at each vertices of octahedron as shown in
following figure. As the ligands approaches to central metal atom (degenerate d-orbitals)
in spherically then degenerate of d-orbitals energy increases.
The degeneracy of d-orbital of central metal is removed by repulsion between electrons
of metal & electrons of ligands.
Octahedral geometry having Central metal M & six ligands at vertices

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Hyderabad. Yours: Dr. B. Shankar
  The energy of d-orbital is splited between eg (dx2-y2 & dz2) & t2g (dxy, dyz, dxz).
 The energy level of eg (dx2-y2 & dz2) is higher than t2g because there experiences strong
repulsion of eg due to approach of ligands along X, Y & Z axis.
 The energy gap (CFSE) between eg & t2g is 10Dq.
 From the figure the energy of eg is higher by 6Dq or 0.6 delta zero from barrier center &
energy of t2g is lower by 4Dq or 0.4 delta zero from barrier center.
 Thus total energy obtained by filling of electrons in eg & t2g gives the value of crystal
field stabilizing energy (CFSE).
 The magnitude of 10 Dq depends on geometry & nature of ligands. For strong field
ligands, splitting would be large & hence value of 10 Dq would be high. For weak field
ligands, splitting would be less & hence value of 10 Dq would be low.
 CFSE in Octahedral Complex = [No. of electrons in t2g (−0.4) +No. of electrons in eg (0.6)]
Δo

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
Let's consider the complexes
1. [Fe(H2O)6]Cl3 (μ = 5.9 B.M.; 5 unpaired electrons),
2. K3[Fe(CN)6] (μ = 1.7 B.M.; 1 unpaired electron).
 Th free Fe3+ ion is a d5 ion. The two complexes are 6-coordinate and octahedral.
HIGH SPIN
 The first three electrons go into t2g orbitals unpaired.
 The 4th and 5th electrons must choose whether to pair up
with electrons already in t2g or to go into higher energy eg
orbitals. In this case, the splitting energy is less, so the 4th
and 5th electrons go into the eg orbitals.

Now let's consider the [Fe(CN)6]3- ion

Again we have five d-electrons. However, there is only one

unpaired electron, so the 4th and 5th electrons must pair with electrons already in t2g
orbitals.

This happens because the octahedral splitting is much greater in the hexacyanoferrate(III) ion
than in the hexaaquoiron(III) ion. That is, the cyanide ligand causes a much greater d-orbital
splitting than water does.
LOW SPIN: The first three e-s go into t2g orbitals as before. The splitting is greater, so e-s to
pair up in the t2g orbitals than to go into the eg orbitals.

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
Crystal field splitting in Tetrahedral Complexes

 Imagine a tetrahedral molecule inside a cube with metal ions in the center of the cube.
The ligands occupy the four alternate corners of the cube leaving the rest four corners empty.
 The g-subscript should be omitted in tetrahedral complexes as these are never
symmetrical.
 In tetrahedral, the ligand approach is in between the axes. The two ‘eg’ (dx2-y2 and dz2)
orbitals point to the center of the face of the cube while the three ‘t2g’ (dxy, dyz and
dzx) orbitals point to the center of the edges of the cube.
 Thus, the t2g -orbitals are nearer to the direction of approach of the ligands than the e-
orbitals.
 So t2g-orbitals energy will increase and eg -orbitals energy will decrease.
 The stability in the complex by the following of electrons in lower energetic eg orbitals is
known as CFSE of tetrahedral complexs
CFSE in Tetrahedral Complex = [No. of electrons in t2g (−0.6) +No. of electrons in eg (0.4)] Δt

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
Magnetic properties of metal ligand complexes
 Many compounds of transition elements show magnetic properties.
 Those which are attracted by magnetic field are termed as paramagnetic while others which are
repelled by magnetic field are called diamagnetic.
 Magnetic properties are determined by the number of unpaired electrons in the d orbitals of the
metal ion.
 Paramagnetic substances are those which contain unpaired electron spins and diamagnetic
substances have paired electron spins.

Calculate CFSE in the following octahedral complexes and also predict

theMagnetic Nature of the complexes:
1) K3[Fe(CN)6]3+ 2) [Fe(H2O)6]Cl3 3) [Co(NH3)6]3+ 4 ) [Co(Cl)6]3-

i) [Ti(H2O)6]3+ ii) [V(H2O)6]2+ iii) [CrCl6]3− iv) [Cr(H2O)6]2+ v) [Cr(H2O)6]3+

vi) [Cr(NH3)6]3+ vii) [Cr(CN)6]3−viii) [MnCl6]4− ix) [Fe(H2O)6]3+ x) [Fe(H2O)6]2+

xi ) [Mn(H2O)6]3+xii) [Mn(H2O)6]2+ xiii) [MnCl6]3− xiv) [Fe(CN)6]4− xv) [Fe(CN)6]3−xvi)

[CoF6]3− xvii) [Co(H2O)6]2+ xviii) [Co(H2O)6]3+ xix) xx) [Co(CN)6]3− xxi) [RhCl6]3−

xxii) [Ni(H2O)6]2+ xxiii) [Ni(NH3)6]2+ xxiv) [Rh(H2O)6]3+ xxv) [Rh(NH3)6]3+

Calculate CFSE in the following tetrahedral complexes also

predict theMagnetic Nature of the complexes:
i) VCl4 ii) [CoCl4]2− iii) [CoBr4]2− iv) [CoI4]2− v) NiCO4

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
Band structure of solids and the role of doping on band structure

In solids, the atoms are arranged in a systematic space lattice and each atom is influenced

by neighboring atoms. The closeness of atoms results in the intermixing of

electrons of neighboring atoms.

Example: Solids are having two types of bands valence band and conductance band.

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
Classifications of materials into Conductors, Semiconductors & Insulators:

Insulators:
In an insulator, the forbidden gap is
Conductance Band
very large and in general is more than
3 Ev.
No electron is available for conduction.
Energy

Forbidden Gap
Large amount of energy is needed to
move electron from, valance band to
conduction band.
Valence Band Ex: wood, stone, rubber, etc.

Filled Band

Semiconductors:
In the case of semiconductors the forbidden
Conduction Band gap is very small.
At 0K the conduction band is empty and
Forbidden gap Around valence band is completely filled.
0.7 Ev(Ge) and 1.1 Ev (Si) When a small amount of energy is supplied,
Energy

the electrons can easily jump the forbidden

gap to conduction band.
Valence Band The conductivity of a semiconductor is of the
order of 102mho cm-2
Ex: Si, Ge, graphite etc
Filled Band

Conductors: In conductors there is no forbidden gap.

The valence band and the conduction band
Conduction Band overlap.
Energy

The electrons from valence band freely enter

No forbidden gap into the conduction Bands.
Therefore very low potential difference can
cause continuous flow of current.
Valence Band Ex: Cu, Al, etc.

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Hyderabad. Yours: Dr. B. Shankar
 Electron and holes in semiconductors:

At 0 k

At absolute o temperature, in a pure

Conduction Band
semiconductor the valence band is completely
Filled and the conduction is vacant.
Electron
Energy

Valence Band

Electrons and holes in semiconductors:

At room temperature
At room temperature, some of the electrons
Conduction Band
Get energy to break the covalent bond and moves
in to the conduction band.
Electron
Energy

Hole

Valence Band

Semiconductors:

Semiconductors are materials whose electronic properties are intermediate between

those of Metals and Insulators. Insulator converted to semiconductors that the substance

at higher temperature covalent band that will be broken due to energy shuffled and relies

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Hyderabad. Yours: Dr. B. Shankar
of electron takes place resulting conduction of electric current.

Semi-Conductors are mainly two type 1) Intrinsic semiconductors (pure)

2) Extrinsic semiconductors (Impure)

Intrinsic semiconductors: A Semiconductor which does not have any kind of impurities
behaves as an Insulator at 0k and behaves as a Conductor at higher temperature is known as

Intrinsic Semiconductor or Pure Semiconductor.

Ex: Germanium & Silicon (4th group elements) and they possess diamond cubic crystalline structure.

Extrinsic semiconductor: These are formed when impurities of certain element are

added to the insulators. This process is known as doping which makes electrons or holes

available for conductivity. Extrinsic semiconductors are two types.

P-type semiconductor and N-type semiconductor

Formation of P-type semiconductor:

The p-type extrinsic semiconductor is formed when a trivalent impurity is an added to a

pure semiconductor in a small amount and as a results, a large number of holes are created in it.
In a p-type semiconductor, most charge carriers are holes while free electrons are a minority.
In P-type semiconductors majority charge carriers are holes.

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
 Si
Complete covalent bond

Si Al Si

Incomplete covalent bond

Presence of hole

Si

Si = extrinsic semiconductor atom

Al = Trivalent impurity atom
Formation of P type extrinsic semiconductor

Formation of N-type material:

Adding the penta-valent impurity to pure semiconductor (like P, As, Sb etc) then it becomes
N-type semiconductor. An n-type extrinsic semiconductor results from implanting dopant
atoms that have more Electron in their outer (bonding) shell then silicon.
The resulting semiconductor crystal contains excess or free electrons that are available
for conducting current. In N-type semiconductors majority charge carriers are electrons.

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar
 Si Si Si Si

Silicon (Si) Adding phosphorus to

Four valences Pure silicon crystal results
Electrons in a surplus electron. And
it becomes a free electron.
Si P Si
Phosphorus (P)
Five valences
Electrons Free electron

P
Si Si Si

Note: In Intrinsic Semiconductor the Number of Conduction electrons will be equal

to the Number of Vacant sites or holes in the valence band.

Sreenidhi University,
Hyderabad. Yours: Dr. B. Shankar