UNIT-1: Periodic Properties and Theories of Bonding

Periodic properties: Electronic configurations, Atomic and ionic sizes, ionization energies, electron-affinity, electro-
negativity (Definition and factors), oxidation states and Penetration of s, p, d and f orbitals.
Crystal field theory (CFT): salient features of CFT- Crystal field splitting patterns of transition metal ion d-orbital in
tetrahedral, octahedral and square planar geometries. Band structure of solids and effect of doping on conductance.
Molecular Orbital Theory: Linear combination of atomic orbitals (LCAO), Molecular orbital Energy level diagrams of
diatomic (N2, O2 and F2). Pi ()-molecular orbitals of Butadiene and Benzene.

Periodicity: The term periodicity is used to indicate that some characteristic properties occur in the
periodic table after definite intervals, however with a varying magnitude. Thus after starting from a certain
point on the periodic table, we are almost certain that the movement in a particular direction will show
steady increase or decrease of a said property.

Electronic configuration: Arrangement or distribution of electrons in the orbitals of an atom. Atom

comprises of subatomic particles like electrons, protons, and neutrons among which only the number of
electrons are considered for electronic configuration. Electrons are filled in such a way that they achieve
a high stable configuration.

Atom consists of s, p, d, and f orbitals in which s orbital can hold a maximum of 2 electrons, p orbital can
hold a maximum of 6 electrons, d orbital can hold a maximum of 10 electrons and f orbitals can hold a
maximum of 14 electrons.

These electrons are filled based on three important laws namely

1. Pauli's exclusion principle
2. Aufbau principle
3. Hund's rule.
Element Electrons Electronic Configuration
Sodium (Na) 11 1s2 2s2 2p6 3s1
Magnesium (Mg) 12 1s2 2s2 2p6 3s2
Aluminum (Al) 13 1s2 2s2 2p6 3s23p1
Silicon (Si) 14 1s2 2s2 2p6 3s23p2

Atomic size: In homo-nuclear diatomic molecules the distance from the centre of one nucleus to the
centre of another nucleus gives the bond length and half of this bond length is atomic radius.
An ion is formed when an atom undergoes a loss or gain of electrons.
M (g)  M+ (g) + e– (cation formation)

M (g) + e–  M– (g) (anion formation)

A cation is formed when an atom loses the most loosely bound electron from its outermost shell.
The atom acquires a positive charge and becomes an ion (a cation).
A cation is smaller than its atom.

1 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

On the removal of an electron, the positive charge of the nucleus acts on lesser number of electrons than
in the neutral atom and thus greater pull is exerted by the nucleus, resulting in a smaller size of the cation.
An anion is bigger than its atom because on receipt of an electron in the outermost orbit the number of
negative charges increase and it outweighs the positive charges, thus the hold of the nucleus on the shells
decrease resulting in an increase in the size of the anion.

A cation is always smaller than its atom and an anion is always bigger than its atom e.g. Na+
is smaller than Na, Cl- is bigger than Cl.

The Radius of Sodium in Its Three Known Oxidation States

Na+ Na0 Na−

Type Cation (+1) Atom (0) Anion (-1)

Electron 1s22s22p6 1s22s22p63s1 1s22s22p63s2

Configuration

Radius (pm) 102 154 202

Ionization Energy/ Ionization Potential: The amount of energy required to remove the most loosely
bound electron from an isolated gaseous atom is called ionization energy (IE).

Ionization energy (IE) is also called as ionization potential (IP) because it is measured as the minimum
potential required to remove the most loosely held electron from the rest of the atom.

IE or IP units: electron volts (eV) per atom or kilo joules per mole of atoms (kJ mol-1).

1 eV per atom = 96.64 kJ mol-1 = 23.05 k cal mol-1

2 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

 Factors affecting Ionization Energy:
1. Size of the atom
2. Charge on the nucleus
3. Screening effect
4. Electronic arrangement
In period: The ionization energy increases with increasing atomic number in a period.
element Li Be B C N O F Ne
Ionization energy 520 899 801 1056 1402 1314 1651 2050

In group: The ionization energy gradually decreases in moving from top to bottom in a group.
element Li Na K Rb Cs
Ionization energy 520 496 419 403 376

Electron Affinity; Electron affinity is the amount of energy released when an electron is added to an
isolated gaseous atom.

Electron affinity is the ability of an atom to hold an additional electron.

If the atom has more tendency to accept an electron then the energy released will be large and
consequently the electron affinity will be high.

Electron affinities can be positive or negative.

It is taken as positive when an electron is added to an atom.

It is expressed as electron volts per atom (eV per atom) or kilo joules per mole.

Variation along a period: The size of an atom decreases and the nuclear charge increases on moving
across a period. This results in greater attraction for the incoming electron. Hence the electron affinity
increases in a period from left to right.

Variation down a group – As we move down a group the atomic size and nuclear size increases. As the
effect of increase in atomic size is more pronounced the additional electron feels less attracted by the
large atom, consequently the electron affinity decreases.

Electronegativity: The relative tendency of an atom in a molecule to attract a shared pair of electrons
towards itself is termed as Electronegativity.

The value of electronegativity of an element describes the ability of its atom to compete for electrons with
the other atom to which it is bonded. Electronegativity is however not the property of an isolated atom.
Electronegativity is measured on a number of scale levels, the most commonly used are of Pauling or
Mullikan.

Factors Affecting Electronegativity

1) Atomic size
2) Ionization energy and electron affinity
3) Number and nature of atoms
4) Type of hybridization
5) Charge on the ion

Variation along a period: As the nuclear charge increases from going left to right in a period because
the electrons enter the same shell, the shielding is less effective.

3 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

 element Li Be B C N O F
electronegativity 1.0 1.5 2 2.5 3 3.5 4

Variation down the group – Electronegativity decreases down the group because the atomic size
increases. The larger the size of the atom the lesser the tendency to attract the shared pair of electrons.
element Li Na K Rb Cs
electronegativity 1 0.9 0.8 0.8 0.7

Oxidation state: Oxidation state of any atom shows the ability of an atom to oxidize (to lose electrons)
or to reduce (to gain electrons) other atoms or species in a chemical compound.
It is related to the number of electrons which an atom loses, gains, or appears to use when bonding with
another atom in a compound.
It’s a difference between the numbers of electrons of the same atom in a compound, as compared with
the number of electrons in an atom of the element.
The oxidation state is the ionic charge on ions and the formal charge in the case of covalent compounds.

Example: NaCl the oxidation states of Na and Cl are +1 and -1

CCl4 the oxidation state of Carbon is (+4) and (-1) for each chlorine.

Example: determining the oxidation states of the elements in the compound KMnO4. By applying rule,
the oxidation state of K = +1 and four oxygen is in -2 state.

Let the oxidation state of Mn = x as manganese can be in several oxidation states.

As the overall charge of the compound is zero. So the algebraic expression can be written as

1+x-8=0

So the oxidation state of manganese is x - 7 = 0 or x = +7.

Similarly the oxidation state of chromium in dichromate ion, (Cr 2O7) 2-.

Since the oxidation state for chromium is not known, so taken it as 2x for chromium
Cr2O7 2-
7(-2)/2 = 14-2 = 12/2 = +6

Examples: OsO4, KMnO4, K2Cr2O7, MnO2, FeSO4, Fe2O3, Fe3O4, FeCl3, MnSO4

Penetration of s, p, d and f orbitals:

4 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

S Orbital:
The s sub shell can hold a maximum of two electrons as there is only one orbital.
S orbitals are spherical in shape and increase in size as the energy level or shell increases.
The order of size is 1s < 2s < 3s <.

P ORBITALS
The p sub shell can hold a maximum of six electrons as there are three orbitals within this sub shell. The
three p orbitals are at right angles to each other and have a lobed shape. The size of the p orbitals also
increases as the energy level or shell increases.

d ORBITALS
There are a total of five d orbitals and each orbital can hold two electrons.
d- orbitals are two groups. The first group contains the dxy, dxz and dyz orbitals.
The second group contains the dx² - y² and dz² orbitals.

5 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

f ORBITALS
At the fourth and higher levels, there are seven f orbitals in addition to the 4s, 4p, and 4d orbitals.

Nature of bonding in complexes are explains three theories,

1. Valence bond theory
2. Crystal Field Theory
3. Molecular orbital Theory

Crystal Field Theory is one of the most important theory for explaining nature of bonding in
coordination compounds.
 It deals with electrostatic interactions between metal ion and the ligands forming complexes with
varying geometries like octahedral, tetrahedral, square planar etc.
 According to this theory, the donor electrons of the incoming ligands due to their negative
charges attract the positively charged metal ion.
 Besides this, there is repulsive interaction between d electrons present on the metal ion and the
ligands.

Certain assumptions are taken while dealing with CFT-

1. The ligands are treated as point charges. Ionic ligands such as Cl-, OH-, CN- are regarded as Negative
(-ve) point charge.
2. The neutral ligands such as H2O, NH3 are regarded as point dipole because these ligands are dipolar.
3. The interactions between metal ion and ligand are treated as purely electrostatic in nature, no
covalent interactions are considered.
4. In complexes shows two types of electrostatic forces a) electrostatic attraction between the metal
cation and the polar ligand. b) The second electrostatic interaction between the lone pair of electrons
on the ligands and the electrons in the d-orbitals of the metal cation.
5. The five (5) d-orbitals in a free metal ion are degenerate (i.e. have same energy). When a complex
is formed, the electrostatic field of the ligands destroy the degeneracy of the d-orbitals. Usually the
complexes formed by transition metal ions are octahedral, tetrahedral or square planar, the field
provided by the ligands is not at all spherically symmetrical therefore d-orbitals are unequally
affected by the ligands.
6. In order to understand the CFT, it is necessary to know the geometry and orientations of the five (5)
d-orbitals.
7. Shape and orientation of d-orbitals:
 dxy, dyz, dzx ( 3 orbitals) lies in between the axes.
 These 3 orbitals lie in xy, yz and zx planes.
 The dx2-y2 orbitals on x and y axes and dz2 orbital on z-axis.
 The shape of dz2 is different from the other four.
 All the 5 orbitals are gerade because the opposite lobes have inversion centre (centre of
symmetry) with respect to phase of wave functions.
 The degenerate d-orbitals split into two degenerate sets, one set consists of lower energy and
more stable dx, dyz and dzx orbitals (t 2g orbitals) and the other less stable higher energy dz2
and dx2-y2 (eg) orbitals.
 The “g” subscript this not used with “t2” and “e” sets in tetrahedral complexes because the
tetrahedral complexes have no inversion centre.
6 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com
Salient features of CFT:
1. Crystal field theory has been developed by Bethe and Vleck.
2. CFT regards a complex as a combination of central metal ion surrounded by other ions or neutral
molecules which are called ligands.
3. The ionic ligands are regarded as point charges.
4. The bonding between metal cations and ligands are purely electrostatic in nature.
5. The electrostatic attraction between the metal ion and ligands are due to the shared pair of
electrons.
6. The electrostatic field of approaching ligands.
7. The interaction between the electrons, cation (central metal ion) and these of ligands are entirely
repulsive.
8. These repulsive forces that are responsible for causing the spilling of d-orbitals of the metal cation.
9. The bond between the metal and the surrounding ligands are purely ionic.
10. If the ligand approaching more towards metal ion, the splitting of d-orbitals more.

Ligand Fields:
Strong ligand field / Low spin: In a strong ligand field, an electrons pair up, and hence  is large
enough to force them to do so and fill the t2g orbitals. Thus in the presence of strong ligand field, the
complex will be low spin.
Eg: NH3 < NO2- < CN- < CO

Weak ligand field / High spin: In a Weak ligand field,  is small, it can’t force the electrons to pair
up and hence the electrons will enter the eg orbitals. Thus in the presence of weak ligand field, the
complex will be High spin.
Eg: I- < Br- < Cl- < NO3- < F-

Spectro chemical series:

When different ligands are arranged in increasing order of o, we get the Spectro chemical series,
(Weak ligand field) I- < Br- < Cl- < NO3- < F- < OH- < EDTA < NH3 < NO2- < CN- < CO (Strong
Ligand field)

Crystal field splitting in octahedral complexes:

In an octahedral complex,
 The ligands approach the central metal atom along the axis, as result the axial orbitals (dz2 and
dx2-y2) experience greater repulsion than non-axial (dx, dy and dz) orbitals.
 The degenerate d-orbitals split into two degenerate sets, one set consists of lower energy and
more stable dx, dyz and dzx orbitals (t 2g orbitals) and the other less stable higher energy dz2
and dx2-y2 (eg) orbitals.
 This splitting of degenerate orbitals under the influence of ligands is termed as crystal field
splitting and the energy separation between them is denoted by “o” where “o” stands for
octahedral.
 The energy of t2g orbitals is decreased by 0.4o or 4 Dq and the energy of eg orbitals rises by
06 o or 6 Dq above the hypothetical degenerate d-orbitals.

7 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

  The crystal field splitting energy o depends on the field produced by the ligand and the charge
on the metal ion.
The crystal field splitting in octahedral complexes is shown as:

 Ligands that produce strong field and causes large splitting are known as strong field ligands.
 Ligands that produce weak field and causes small degree of splitting are known as weak field
ligands.
 The magnitude of o and the distribution of electrons in the d-orbitals is largely influenced by
the ligand field strength.
Crystal field splitting in Tetrahedral Complexes:
 A regular tetrahedral geometry is obtained when a metal cation or atom is placed the centre of
a cube and 4 ligands occupy the alternate corners of the cube.
 The x, y and z axes are passed through the centre of the faces of the cube.
 None of the ligands approaches directly any of the metal d-orbitals.
 Instead they all approach to some degree in between the metal d-orbitals.
 The crystal field splitting in tetrahedral complex is denoted by “t”, where “t” stands for
tetrahedral.
The crystal field splitting in tetrahedral complexes is shown as

8 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

  The dxy, dyz and dzx orbitals of metal cation, experience more repulsion from the ligands and
are of higher energy than those of the dx2-y2 and dz2 orbitals.
 The dxy, dyz and dzx orbitals (“t 2” set orbitals) are 0.4 t above the bary-centre and the dx2-
y2 and dz2 (“e” set) orbitals are 0.6 t below the bary-centre. Therefore the energy of t2 orbital
is raised and “e” set orbitals is lowered from the center. The “g” subscript this not used with
“t2” and “e” sets because the tetrahedral complexes have no inversion centre.
 It has been observed that the energy separation between “e” and “t2” orbitals in tetrahedral
complexes is smaller than in octahedral complexes, because d-orbitals are not directly under
the influence of the ligand and the number of ligands is smaller.

Square planar complex:

In a square planar complex, there are four ligands around the metal ion.
The electrons of ligands are only attracted to xy-plane.
Any orbital in the xy-plane has a higher energy level.
So, the dx2-y2 and dxy orbitals energy will be increases and dz2 & dzx orbital energy will be decreases.
Thus in square planar geometry, the order of energy of different d-orbitals
Dyz = dzx < dz2 < dxy < dx2-y2
The crystal field splitting in SP complex is denoted by “sp”.
The values of sp has been found to be greater than o because the dyz, dzx orbitals interact with
two ligands in the sp complex while in octahedral complexes the interactions takes place with 4
ligands sp has been found equal to 1.3 o

9 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

 MOLECULAR ORBITAL THEORY
In the VBT, the individuality of atomic properties of the constituting atoms forming a molecule is retained
too some extent. Whereas, in the molecular orbital theory it is considered that molecular orbitals are
formed by the linear combination of the two constituting atomic orbitals wave functions.
A Molecular orbital (MO) is constructed by combination of two Atomic orbitals (AO’s) and this method
is known as Linear combination of Atomic orbitals (LCAO).
Linear combination of Atomic orbitals (LCAO):
1. Electrons may be considered either as particle or wave. An electrons in an atom may therefore be
described by a wave function(), which is a solution to schrodinger wave equation.
2. According to Molecular orbital Theory(MOT) the electrons in a molecule are said to occupy
Molecular orbitals (MO’s)
3. The wave function describing a Molecular orbitals (MO’s) may be obtained by the method of
LCAO.
Let us consider, ψ(A) and ψ(B) are two atomic orbitals which are combining to form Molecular orbitals
(MO’s) for A-B bond.
molecular orbitals will also be wave functions and they can be represented as:
ψ(Mob) = ψ(A) + ψ(B) ψ(Mob) = bonding molecular orbital wave function
ψ(Moab) = ψ(A) - ψ(B) ψ(Moab) = anti bonding molecular orbital wave function
The MOT given by R. S. Mullican and F. Hund incorporates the following points:
1. When nuclei of two atoms comes close to each other, their Atomic orbitals (AO’s) interacts, to
form Molecular orbitals (MO’s) in which the identity of both the atomic orbitals is lost.
2. The number of Molecular orbitals (MO’s) is equal to the number of Atomic orbitals (AO’s)
involved in their formation.
3. Just as Atomic orbitals in an atom are quantized, similarly Molecular orbitals (MO’s) are also
believed to be quantized.
4. The electrons in the Atomic orbitals (AO’s) are influenced by one nucleus, the electrons in the
Molecular orbitals (MO’s) are influenced by all the nuclei.
5. Electrons are filled in the Molecular orbitals (MO’s) in the same way as they are filled in Atomic
orbitals (AO’s), following Aufbau principle, Hund’s rule of maximum multiplicity.
6. The Molecular orbitals are represented by ϭ, ϭ*, ∏, ∏*etc.

Bonding Molecular orbitals: They are formed by the additive effect of the Atomic orbitals (AO’s).
ψ(Mob) = ψ(A) + ψ(B) ψ(Mob) = bonding molecular orbital wave function
It increases the electron density between the nuclei. These orbitals have lower energy than the Atomic
orbitals (AO’s) from which they are formed.
Bonding Molecular orbitals stabilizes the molecule, these are represented by ϭ, ∏ etc.
Anti-Bonding Molecular orbitals: They are formed by the substractive effect of the Atomic orbitals
(AO’s).
ψ(Moab) = ψ(A) - ψ(B) ψ(Moab) = anti bonding molecular orbital wave function

10 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

It decreases the electron density between the nuclei. These orbitals have higher energy than the Atomic
orbitals (AO’s) from which they are formed.
Anti-Bonding Molecular orbitals destabilizes the molecule, these are represented by ϭ*, ∏* etc.
The order of energy of Molecular orbitals (MO’s) has been determined from spectroscopic data.
The energy generally increases in the following order as we move from left to right.
Ϭ1s Ϭ*1s Ϭ2s Ϭ*2s Ϭ2pz∏2px = ∏2py ∏*2px = ∏*2py  Ϭ*2pz
In the case of homo nuclear diatomic molecules of second row element of the periodic table up to N 2,
the Ϭ2pz orbitals are higher energy than the ∏2px = ∏2py Molecular orbitals. For these atoms the
order is:
Ϭ1s Ϭ*1s Ϭ2s Ϭ*2s ∏2px = ∏2py  Ϭ2pz∏*2px = ∏*2py  Ϭ*2pz
Filling of electrons in Molecular orbitals in MOT: For simple homo atomic molecules, the filling of
electrons are carried out in a similar fashion as in atomic orbitals.
Following rules are followed:
1. Aufbau principle: the orbitals with lowest energy is to be filled first of all. i.e., electrons enter
various molecular orbitals in the order of their increasing energies.
2. Pauli Exclusion Principle: the maximum number of electrons in a molecular orbitals cannot
exceed two and these should have opposite spins.
3. Hund’s rule: pairing of electrons takes place only when each molecular orbitals of the same
energy has at least one electron each.
4. A bond between two atoms is said to be found when the total number of electrons in bonding
orbitals is greater than the number of anti bonding orbitals.
5. Bond order (BO): BO is defined as half of the difference between the number of electrons
present in the bonding and the anti bonding orbitals.
Bond order (BO) = ½ [Number of bonding orbital electrons - Number of anti-bonding
orbital electrons]

11 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

N2 : Ϭ1s2 Ϭ*1s2 Ϭ2s2 Ϭ*2s2 ∏2px2 = ∏2py2  Ϭ2pz2∏*2px = ∏*2py  Ϭ*2pz

12 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

O2 : Ϭ1s2 Ϭ*1s2 Ϭ2s2 Ϭ*2s2 Ϭ2pz2∏2px2 = ∏2py2 ∏*2px1 = ∏*2py1  Ϭ*2pz

13 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

F2 : Ϭ1s2 Ϭ*1s2 Ϭ2s2 Ϭ*2s2 Ϭ2pz2∏2px2 = ∏2py2 ∏*2px2 = ∏*2py2  Ϭ*2pz
Pi – molecular orbitals of Butadiene:
1,3-Butadiene is composed of 4 carbons with two adjacent  bonds. These  bonds are conjugated. All
the four p orbitals are aligned with each other and build up into a larger  system.
The structure of 1,3-Butadiene consists of two double bonds. The structure has four sp 2 hybridized C
atoms. Each atom contributes a p atomic orbital consisting of one electron.

14 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

The combination of pi () molecular orbitals of two ethane molecules produce pi () molecular orbitals
for which we need to make an in-phase and an out-of-phase combination for pi () and pi* (*) of
ethane.

The ∏ Molecular Orbitals of Benzene

Each molecular orbital of benzene consist of a combination of the sic p orbitals. Bonding interactions
occurs when the orbitals to line up in a way that each lobe overlapping another p orbital has same signs.
An orbital lining up with an opposite sign creates an anti-bonding interaction and a node between the
orbitals.
The 3  bonds of benzene are formed by the overlapping of 6 p orbitals on 6 adjacent carbon atoms. The
6 p orbitals form 6 molecular orbitals by combining in 6 different ways. The 6 MOs are designated by
1, 2, 3, *4, *5, *6 of these 6 MOs. 1, 2, 3 are bonding molecular orbitals whereas *4, *5,
*6 are anti-bonding molecular. Each MO can accommodate 2 electrons having opposite spin.
Therefore, addition of 6 electrons to the molecular orbitals beginning from the lower energy molecular
orbital results in the filling of all 3 bonding MOs. The 3 higher energy antibonding orbitals remain empty.
Due to the presence of 3 filled bonding MOs in benzene, it possesses a closed bonding shell which makes
benzene stable.

15 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

16 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com
 BAND STRUCTURE OF SOLIDS
This is the quantum mechanical treatment of the metallic bond and is similar to molecular orbitals approach of
covalent bond. Unlike simple covalent molecules during formation of metallic crystals, a very large number of
atoms in the order of 1023 or more are brought together so that their atomic orbitals undergo linear combination to
form exactly same number of molecular orbitals.
The energies of these molecular orbitals are so closely spaced that they appears to be a continuum known as quasi-
continuous energy band. Hence it is known as band structure of solids.
The molecular orbitals formed are delocalized, i.e., belong to the crystal as a whole. The band gap/fermi level is
shown in figure:

Let us look in to a specific example of Lithium metal. The electronic configuration of Li is 1s2 2s1 2p0 when n-Li
atoms come close to form Li crystal, 3 energy bands are formed.
1s band: This band is formed by combination of large number of ‘1s’ atomic orbitals of Li atoms and hence
contains n number of energy levels. This band is completely filled and carries 2n electrons. This is inner shell band
and is not influenced by surrounding atoms, therefore narrow at equilibrium interatomic distance.
2s band: This band is formed by combination of ‘2s’ orbitals of n atoms. This band has n levels. This band is half
filled and contains ‘n-electrons’. The upper half remains vacant. This is a valency band and is significantly
influenced by surrounding atoms. It is quite spared out at equilibrium distance. Due to close spacing of energy
levels, electrons can move to energy levels in upper half at room temperature.
2p band: n atoms of Li give 3n levels in 2p band. 2s and 2p levels are so close in energy that the bands overlap
and the electrons pf 2s band gets additional energy levels differing slightly in energies to move about. The total
capacity of this overlapped band is 8n electrons and is therefore 1/8 th filled.
Effect of doping on conductance:
Doping is nothing but adding N or P type impurities to a pure semiconductor. So these impurities will contain
electrons or holes based on their impurity. When these kind of doping takes place in semiconductors and voltage
is applied, these electrons will conduct electricity. In case of holes, electrons due to potential excitation jump from
their original positions to these holes and form immobile ions at that point, whereas equal amount of holes are
created from where these electrons jumped. Thus conductivity increases due to doping.

Doping means the introduction of impurities into a semiconductor crystal to the defined modification of
conductivity. Two of the most important materials silicon can be doped with, are boron (3 valence electrons = 3-
valent) and phosphorus (5 valence electrons = 5-valent). Other materials are aluminum, indium (3-valent) and
arsenic, antimony (5-valent).

17 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com

The dopant is integrated into the lattice structure of the semiconductor crystal, the number of outer electrons define
the type of doping. Elements with 3 valence electrons are used for p-type doping, 5-valued elements for n-doping.
The conductivity of a deliberately contaminated silicon crystal can be increased by a factor of 10 6.

Doped semiconductors are electrically neutral. The terms n- and p-type doped do only refer to the majority charge
carriers. Each positive or negative charge carrier belongs to a fixed negative or positive charged dopant.

N- and p-doped semiconductors behave approximately equal in relation to the current flow. With increasing amount
of dopants, the number of charge carriers increases in the semiconductor crystal. Here it requires only a very small
amount of dopants. Weakly doped silicon crystals contain only 1 impurity per 1,000,000,000 silicon atoms, high
doped semiconductors for example contain 1 foreign atom per 1,000 silicon atoms.

By the introduction of a dopant with five outer electrons, in n-doped semiconductors there is an electron in the
crystal which is not bound and therefore can be moved with relatively little energy into the conduction band. Thus
in n-doped semiconductors the donator energy level is close to the conduction band edge, the band gap to overcome
is very small.

Analog, through introduction of a 3-valent dopant in a semiconductor, a hole is available, which may be already
occupied at low-energy by an electron from the valence band of the silicon. For p-doped semiconductors the
acceptor energy level is close the valence band.
When we add impurities to semiconductors we call them dopants and the process is called doping. The result is
a dilute (100 -1000 ppm) substitutional solid solution.
Band model of doped semiconductors

More info…

Visit…. Sreechemistry.blogspot.in

18 UNIT-1: Periodic Properties and Theories of Bonding: srichemistry@gmail.com