NAME: KUSHAL MAURYA

CLASS: M. SC CHEMISTRY-I

ROLL NO: 07

SEMESTER: I

SUBJECT: INORGANIC CHEMISTRY

COLLEGE: SATHAYE COLLEGE

Topic: 3.1 Electronic Structures of Solid and Band Theory, Fermi level and Brillouin
Zones.
Sr.no Index

1. Introduction

2. Electronic Structure of Solids

3. Band Theory

4. The Fermi level

5. The Brillouin zones

6. References
● INTRODUCTION
The electronic structure of solids, as described by band theory, is a fundamental concept in condensed
matter physics and materials science. Unlike isolated atoms, where electrons occupy discrete energy
levels, electrons in a solid are delocalized and form energy bands. Band theory explains how these energy
bands are formed by the overlapping atomic orbitals of neighbouring atoms in a crystal lattice. Within
these bands, electrons have varying energy levels, and there are specific bands, such as valence and
conduction bands, that are crucial for understanding a material's properties. The valence band is the
highest energy band filled with electrons at absolute zero temperature, while the conduction band is the
next higher energy band where electrons can move freely. The energy gap between these bands, known as
the band gap, determines a material's electrical conductivity: materials with a large band gap are
insulators, while those with a small or no band gap are conductors or semiconductors.

● Electronic Structures of Solids

The conductivities of inorganic solids:

Key points: A metallic conductor is a substance with an electric conductivity that decreases with
increasing temperature; a semiconductor is a substance with an electric conductivity that
increases with increasing temperature.

The molecular orbital theory of small molecules can be extended to account for the properties of solids,
which are aggregations of an almost infinite number of atoms. This approach is strikingly successful for
the description of metals; it can be used to explain their characteristic lustre, their good electrical and
thermal conductivity, and their malleability. All these properties arise from the ability of the atoms to
contribute electrons to a common ‘sea’. The lustre and electrical conductivities stem from the mobility of
these electrons in response to either the oscillating electric field of an incident ray of light or to a potential
difference. The high thermal conductivity is also a consequence of electron mobility because an electron
can collide with a vibrating atom, pick up its energy, and transfer it to another atom elsewhere in the solid.
The ease with which metals can be mechanically deformed is another aspect of electron mobility because
the electron sea can quickly readjust to a deformation of the solid and continue to bind the atoms
together.

Electronic conduction is also a characteristic of semiconductors. The criterion for distinguishing between
a metallic conductor and a semiconductor is the temperature dependence of the electric conductivity
(Fig.1.).

A metallic conductor is a substance with an electric conductivity that decreases with increasing
temperature.

A semiconductor is a substance with an electric conductivity that increases with increasing temperature.
 It is also generally the case (but not the criterion for distinguishing them) that the conductivities of metals
at room temperature are higher than those of semiconductors. Typical values are given in Fig.1. A solid
insulator is a substance with a very low electrical conductivity. However, when that conductivity can be
measured, it is found to increase with temperature, like that of a semiconductor. For some purposes,
therefore, it is possible to disregard the classification ‘insulator’ and to treat all solids as either metals or
semiconductors.

Superconductors are a special class of materials that have zero electrical resistance below a critical
temperature.

Fig.1. The variation of the electrical conductivity of a substance with temperature is the basis of the classification of
the substance as a metallic conductor, a semiconductor, or a superconductor.

● BAND THEORY OF SOLIDS

i) Bands formed from overlapping atomic orbitals:

The central idea underlying the description of the electronic structure of solids is that the valence
electrons supplied by the atoms spread through the entire structure. This concept is expressed more
formally by making a simple extension of MO theory in which the solid is treated like an indefinitely large
molecule. In solid-state physics, this approach is called the tight-binding approximation. The description
in terms of delocalized electrons can also be used to describe non-metallic solids. We therefore begin by
showing how metals are described in terms of molecular orbitals. Then we go on to show that the same
principles can be applied, but with a different outcome, to ionic and molecular solids.

ii) Band formation by orbital overlap:

Key point: The overlap of atomic orbitals in solids gives rise to bands of energy levels separated by
energy gaps.

The overlap of many atomic orbitals in a solid lead to many molecular orbitals that are closely spaced in
energy and so form an almost continuous band of energy levels (Fig.2). Bands are separated by band
gaps, which are values of the energy for which there is no molecular orbital.

The formation of bands can be understood by considering a line of atoms, and supposing that each atom
has an s orbital that overlaps the s orbitals on its immediate neighbours (Fig.3). When the line consists of
only two atoms, there is a bonding and an antibonding molecular orbital. When a third atom joins them,
there are three molecular orbitals.

The central orbital of the set is nonbonding and the outer two are at low energy and high energy,
respectively. As more atoms are added, each one contributes an atomic orbital, and hence one more
molecular orbital is formed. When there are N atoms in the line, there are N molecular orbitals. The
orbital of lowest energy has no nodes between neighbouring atoms. The orbital of highest energy has a
node between every pair of neighbours. The remaining orbitals have successively 1, 2… internuclear
nodes and a corresponding range of energies between the two extremes.

The total width of the band, which remains finite even as N approaches infinity (as shown in Fig.4),
depends on the strength of the interaction between neighbouring atoms. The greater the strength of
interaction (in broad terms, the greater the degree of overlap between neighbours), the greater the energy
separation of the non-node orbital and the all-node orbital. However, whatever the number of atomic
orbitals used to form the molecular orbitals, there is only a finite spread of orbital energies (as depicted in
Fig.4).

It follows that the separation in energy between neighbouring orbitals must approach zero as N
approaches infinity, otherwise the range of orbital energies could not be finite. That is, a band consists of a
countable number but near-continuum of energy levels.

The band just described is built from s orbitals and is called an s band. If there are p orbitals available, a p
band can be constructed from their overlap as shown in Fig.5.
Fig.2. The electronic structure of a solid Fig.3. A band can be thought of as

is characterised by a series of bands of formed by bringing up atoms successively

orbitals separated by gaps at energies to form a line of atoms. N atomic orbitals

where orbitals do not occur. give rise to N molecular orbitals.

Fig.4. The energies of the orbitals that Fig.5. An example of a p band in a

are formed when N atoms are brought one-dimensional solid.

up to form a one- dimensional array.

 Because p orbitals lie higher in energy than s orbitals of the same valence shell, there is often an energy
gap between the s band and the p band (Fig.6). However, if the bands span a wide range of energy and the
atomic s and p energies are similar (as is often the case), then the two bands overlap. The d band is
similarly constructed from the overlap of d orbitals. The formation of bands is not restricted to one type of
atomic orbital and bands may be formed in compounds by combinations of different orbital types, for
example the d orbitals of a metal atom may overlap the p orbitals of neighbouring O atoms.

Fig.6. (a) The s and p bands of a solid and the gap between them. Whether or not there is in fact a gap depends on
the separation of the s and p orbitals of the atoms and the strength of the interaction between them in the solid. (b) If
the interaction is strong, the bands are wide and may overlap.

● The Fermi levels

Key point: The Fermi level is the highest occupied energy level in a solid at T=0.

At T=0, electrons occupy the individual molecular orbitals of the bands in accordance with the building-up
principle. If each atom supplies one’s electron, then at T=0 the lowest 1/2N orbitals are occupied. The
highest occupied orbital at T=0 is called the Fermi level; it lies near the centre of the band (Fig.7). When
the band is not completely full, the electrons close to the Fermi level can easily be promoted to nearby
empty levels. As a result, they are mobile and can move relatively freely through the solid, and the
substance is an electrical conductor.

The solid is in fact a metallic conductor. We have seen that the criterion of metallic conduction is the
decrease of electrical conductivity with increasing temperature. This behaviour is the opposite of what we
might expect if the conductivity were governed by thermal promotion of electrons above the Fermi level.
The competing effect can be identified once we recognize that the ability of an electron to travel smoothly
through the solid in a conduction band depends on the uniformity of the arrangement of the atoms.

An atom vibrating vigorously at a site is equivalent to an impurity that disrupts the orderliness of the
orbitals. This decrease in uniformity reduces the ability of the electron to travel from one edge of the solid
 to the other, so the conductivity of the solid is less than at T=0. If we think of the electron as moving
through the solid, then we would say that it was ‘scattered’ by the atomic vibration.

This carrier scattering increases with increasing temperature as the lattice vibrations increase, and the
increase accounts for the observed inverse temperature dependence of the conductivity of metals.

Fig.7. If each of the N atoms supplies one’s electron, then at T=0 the lower ½N orbitals are occupied and the Fermi
level lies near the centre of the band.

● The Brillouin zones

Leon Brillouin (1889-1969) first introduced Brillouin Zones in his work on the general properties of
periodic structures. The concept and construction of the zones can appear quite abstract, but this is
largely a result of their wide range of useful applications.

Brillouin zones are polyhedral in reciprocal space in crystalline materials and are the geometrical
equivalent of Wigner-Seitz cells in real space. Physically, Brillouin zone boundaries represent Bragg planes
which reflect (diffract) waves having wave vectors so that they cause constructive interference.
The reciprocal lattices (dots) and corresponding first Brillouin zones of (a) square lattice and (b) hexagonal lattice.

The first Brillouin zone is the smallest volume entirely enclosed by planes that are the perpendicular
bisectors of the reciprocal lattice vectors drawn from the origin. The concept of Brillouin zone is
particularly important in the consideration of the electronic structure of solids. There are also second,
third, etc., Brillouin zones, corresponding to a sequence of disjoint regions (all with the same volume)
at increasing distances from the origin, but these are used more rarely. As a result, the first Brillouin
zone is often called simply the Brillouin zone. (In general, the n-th Brillouin zone consist of the set of
points that can be reached from the origin by crossing n − 1 Bragg planes.)

The region in k-space (here an imaginary plane whose rectangular coordinates are kx and ky) that low-k
electrons can occupy without being diffracted is called first Brillouin Zone. As shown in figure1. The
second Brillouin zone is also Shown; it contains electrons with k values from π/a to 2π/a for electrons
moving in the ±x and ±y directions, with the possible range of k values narrowing as the diagonal
directions are approached.

Further Brillouin zones can be constructed in the same manner. The extension of this analysis to
three-dimensional structure leads to Brillouin zones such as those shown in the Figure 2.

Fig. 1. The first and second Brillouin zones Fig.2. The first three Brillouin zones for some

of a two-dimensional square lattice. lattices are illustrated.

● References

1. B. R. Puri, L. R. Sharma, and K. C. Kalia, Principles of Inorganic Chemistry, Milestone Publishers,

2013-2014

2. P.A. Cox, The electronic structure and chemistry of solids. Oxford University Press (1987).

3. https://en.m.wikipedia.org/wiki/Brillouin_z one.