MOLECULES AND SOLIDS

TOPICS
•Molecular bonds
•Energy states and spectra of molecules
•Bonding in solids
•Free-electron theory of metals
•Band theory of solids
•Electrical conduction in metals, insulators
and semiconductors
•Semiconductor devices
•Superconductivity

Text Book
PHYSICS for Scientists and Engineers
with Modern Physics (6th ed)
By Serway & Jewett
1
 MOLECULAR BONDS
The bonding mechanisms in a molecule are fundamentally
due to electric forces between atoms (or ions), but these
forces are more complex than the simple Coulomb attraction
or repulsion between single charges.

The forces between the components of a molecule are

related to a potential energy function which has a
minimum value in a stable molecule. This potential
energy function should account for the two features of
molecular bonding:

MIT- MANIPAL 2
The force between atoms is repulsive at very small
separation distance.

When two atoms are brought close to each other, some of

their electron shells overlap, resulting in repulsion between
the shells.

The repulsive force between the atoms at very small

separation distance is partly due to electrostatic forces
and partly the result of the exclusion principle.

For the separation distances slightly larger than that

corresponding to a stable molecule, the force between
atoms is attractive due to dipole-dipole interaction
between charge distributions within the atoms of the
molecule.
3
 MOLECULAR BONDS
Hence the potential energy for a system of two atoms
is of the form

r = internuclear separation
distance between the two
atoms.
n and m are small integers.
The negative term is
associated with attractive
force and the positive term
with repulsive force.
At equilibrium separation
distance of r (= bond-length),
U is minimum.
4
 MOLECULAR BONDS
Ionic Bonding: An ionic bond is formed by electrostaic
attraction between oppositely charged ions. Eg, NaCl.
Ionization energy of Na is 5.1 eV. The electron affinity
of Cl is 3.7 eV. Thus, the energy required to form
Na+and Cl– ions from the neutral atoms is 5.1 – 3.7 =
1.4 eV. This is the total energy of NaCl molecule
when the ions infinitely apart. This energy decreases
to minimum (–4.2 eV) at the equilibrium separation
distance (0.24 nm).
Hence , the dissociation
energy of NaCl is
4.2 eV.

MIT- MANIPAL 5
 Na + Cl → Na+ + Cl− → NaCl

MIT-MANIPAL 6
 MOLECULAR BONDS
Covalent Bonding: In covalent bond the electrons
supplied by either one or both atoms are shared by the
two atoms. Eg: H2, F2, CO.
To describe covalent bonds in H2 by atomic wave
functions, consider H-atom ground state wave function:

Graph of wave functions for

two H-atoms:
Overlap of wave functions for
two H-atoms close together
indicates high probability
amplitude for the electrons
between the atoms:
MIT- MANIPAL 7
 MOLECULAR BONDS

It appears as a fixed negative

charge between the atoms
exerting attractive force on
both the H-nuclei. The
result is a overall attractive
force between the atoms
resulting in a covalent bond.

MIT- MANIPAL 8
 MOLECULAR BONDS
Van der Waals Bonding: Van der Waals forces are
weak attractive forces (electrostatic) between neutral
molecules or neutral atoms which do not form ionic or
covalent bonds.

These forces are due to the electric dipole interactions.

It is due to these van der Waals bonds, the inert
gases can be condensed to form solids at atmospheric
pressure.

The three types of van der Waals forces are dipole-

dipole force, dipole-induced dipole force and dispersion
force.

MIT- MANIPAL 9
 MOLECULAR BONDS
Hydrogen Bonding: A hydrogen bond is a weak
electrostatic chemical bond which forms between
covalently bonded H-atoms and a strongly
electronegative atom with a lone pair of electrons (eg: O,
N, F).

In the two covalent bonds in H2O, the electrons from the H-

atoms are more likely to be found near the O-atom than
near the H-atoms. Thus the protons (H-nuclei) are
unshielded by electrons and can be attracted to the negative
end of another polar molecule (eg: O of H2O). This way
hydrogen is formed between two H2O molecules. This bond
is strong enough to form a solid crystalline structure (ice).
Similarly, DNA molecules are held together by N–H - - - N
hydrogen bonds.
MIT- MANIPAL 10
 MOLECULAR BONDS
SJ-PROBLEM 43.1: A K+ ion and a Cl– ion are
separated by a distance of 5.00 x 10–10 m. Assuming the
two ions act like point charges, determine
(a)the force each ion exerts on the other and
(b) the potential energy of the two-ion system in
electron volts.

Solution (a)

Solution (b)

11
 MOLECULAR BONDS
SJ-PROBLEM 43.3: The potential energy (U) of a
diatomic molecule is given by Lennard-Jones potential:

where A and B are constants.

Find, in terms of A and B, (a) the value of ro at which
the energy is minimum and
(b)the energy E required to break up a diatomic
molecule.
(c) Evaluate ro in metres and E in electron-volts for the
H2 molecule.
Take A = 0.124 x 10–120 eV.m12 and
B = 1.488 x 10–60 eV.m6.
MIT- MANIPAL 12
Solution (a)

Solution (b)

Solution (c)

13
 ENERGY STATES AND SPECTRA OF MOLECULES
The energy of an isolated molecule can be divided into
four categories: (1) electronic energy, due to the
interactions between the molecule’s electrons and nuclei;
(2) translational energy, due to the motion of molecule’s
centre of mass through space; (3) rotational energy, due
to the rotation of the molecule about its centre of mass;
and (4) vibrational energy, due to the vibration of the
molecule’s constituent atoms:

E = EEL + ETRANS + EROT + EVIB

The ETRANS is unrelated to the internal structure of

the molecule, this molecular energy of a molecule is
unimportant in interpreting molecular spectra. The
EROT and EVIB give spectral lines in microwave and the
infrared regions of the electromagnetic spectrum,
respectively. 14
 ENERGY STATES AND SPECTRA OF MOLECULES
Rotational motion of molecules: A diatomic molecule
(m1, m2= masses of the atoms, r = internuclear
separation) aligned along an x-axis has only two
rotational degrees of freedom, corresponding to rotations
about the y- and z-axes.
ω= angular frequency of
rotation about y-axis or z-axis
EROT = rotational kinetic energy of the
molecule about that axis

Moment of inertia of
the diatomic molecule
Reduced mass of
the diatomic
molecule
Magnitude
MIT- MANIPAL of the classical angular momentum, L = I ω 15
 ENERGY STATES AND SPECTRA OF MOLECULES
Rotational motion of molecules:
Quantized angular momentum of the molecule
J = 0, 1, 2, . . . = rotational
quantum number

The rotational energy of the molecule is

quantized and depends on its moment of
inertia. Quantized rotational energies of a
diatomic molecule 16
 ENERGY STATES AND SPECTRA OF MOLECULES
Rotational motion of molecules:
Selection rule for rotational transitions: ∆J = ±1

Rotational transition photon energies:

J = 1, 2, 3, . . .
f2 = 2 f1 , f3 = 3 f1, and so on

These occur in the microwave region.

Quantized rotational energies of a

diatomic molecule.
17
 ENERGY STATES AND SPECTRA OF MOLECULES
SJ-EXAMPLE 43.1: Rotation of the CO molecule:
The J = 0 to J = 1 rotational transition of the CO
molecule occurs at a frequency of 1.15 x 1011 Hz.

(A)Use this information to calculate the moment of

inertia of the molecule.
(B)Calculate the bond-length of the molecule.

MIT- MANIPAL 18
Solution (A)

Solution (B) I=μr2

19
 ENERGY STATES AND SPECTRA OF MOLECULES
SJ-PROBLEM 43.7: An HCl molecule is excited to its
first rotational energy level, corresponding to J = 1. If
the distance between its nuclei is ro = 0.1275 nm, what
is the angular speed (ω) of the molecule about its
centre of mass ?

MIT- MANIPAL 20
21
 ENERGY STATES AND SPECTRA OF MOLECULES
Vibrational motion of molecules: Plot of potential
Model of a diatomic energy function
molecule as a simple for a diatomic
harmonic oscillator molecule
ro =EQUILIBRIUM
SEPARATION

For values of r close to ro U varies as square of the

displacement from equilibrium, like that of a simple
harmonic oscillator.
According to classical mechanics, the
frequency of vibration is
k = effective spring constant
μ = reduced mass 22
 ENERGY STATES AND SPECTRA OF MOLECULES
Vibrational motion of molecules:
According to quantum mechanics the vibrational motions
are quantized. The allowed vibrational energies of the
quantum harmonic oscillator are
v EVIB

5
v = vibrational quantum number
f = frequency of the oscillator 4
The lowest vibrational state has the
energy = (½) hf. 3
Substitute
2
EVIB ΔEVIB
1

Selection rule for the allowed vibrational 0

transitions: Δv = ±1 23
 ENERGY STATES AND SPECTRA OF MOLECULES
Vibrational motion of molecules:
Vibrational transition photon energies:

v EVIB

f = frequency of the oscillator. 5

These photons are in infrared region of
the spectrum. 4

At room temperature most molecules 3

have vibrational energies corresponding
to the v = 0 state because the spacing 2
between vibrational states is much EVIB ΔEVIB
greater than the thermal energy (kBT) at 1

room temperature. 0
MIT- MANIPAL 24
 ENERGY STATES AND SPECTRA OF MOLECULES
SJ-EXAMPLE 43.2: Vibration of the CO molecule:
The frequency of photon that causes v = 0 to v = 1
transition in the CO molecule is 6.42 x 1013 Hz.
Ignore any changes in the rotational energy.
v EVIB
(A) Calculate the force constant k for this
molecule. 5
(B)What is the maximum
classical amplitude of vibration for this 4 molecule
in the v = 0 vibrational state ?
3

2
EVIB ΔEVIB
1

0
25
Solution (A)

26
Solution (B)

27
 ENERGY STATES AND SPECTRA OF MOLECULES
SJ-PROBLEM 43.13: Taking the effective force
constant of a vibrating HCl molecule as k = 480 N/m,
find the energy difference between the ground state
and the first excited vibrational energy level.
v EVIB

2
EVIB ΔEVIB
1

0
28
 ENERGY STATES AND SPECTRA OF MOLECULES
Molecular spectra:
In general a molecule vibrates and rotates simultaneously.
So, for a molecule the total energy is the sum of its
vibrational energy and rotational energy

MIT- MANIPAL 29
 EXPECTED LINES IN THE
ABSORPTION SPECTRUM OF A
DIATOMIC MOLECULE

ABSORPTIVE TRANSITIONS
BETWEEN V = 0 AND V = 1
VIBRATIONAL STATES OF A
DIATOMIC MOLECULE WITH
CONDITION ΔJ = ±1

WHEN A MOLECULE ABSORBS A

PHOTON OF FREQ (f), THE
VIBRATIONAL QUANTUM NUMBER V
INCREASES BY ONE UNIT WHILE
ROTATIONAL QUANTUM NUMBER J
EITHER INCREASES OR DECREASES
BY ONE UNIT.

SO, MOLECULAR SPECTRUM

CONSISTS OF TWO GROUPS OF
LINES.
30
 ENERGY STATES AND SPECTRA OF MOLECULES
Molecular spectra:
The energies of the absorbed
photon of freq ‘f’:

J = rotational quantum number

of the initial state.

ADJACENT SPECTRAL LINES ARE

SEPARATED BY FREQUENCY:

31
 ENERGY STATES AND SPECTRA OF MOLECULES
Molecular spectra:
ABSORPTION SPECTRUM OF THE
HCl MOLECULE

THE DOUBLET IN EACH PEAK IS

DUE TO THE TWO ISOTOPES OF
Cl

SPECTRAL LINES
EQUALLY SPACED 32
 ENERGY STATES AND SPECTRA OF MOLECULES
SJ-PROBLEM 43.19: An H2-molecule is in its
vibrational and rotational ground states. It absorbs a
photon of wavelength 2.2112 μm and jumps to the v
= 1, J = 1 energy level. It then drops to the v=
0, J = 2 energy level, while emitting a photon of
wavelength 2.4054 μm.
Calculate J=2
(a)the moment of inertia of the H2- V=1 J=1
J=0
molecule about an axis through its

λ=2.4054 μm
λ=2.2112 μm
centre of mass and perpendicular
to the H-H bond
(b)the vibrational frequency of the H2-
J=2
molecule. V=0 J=1
(e)the equilibrium separation distance J=0
for this molecule.
33
Solution (a)
J=2
V=1 J=1
J=0

λ=2.4054 μm
λ=2.2112 μm
J=2
(1) V=0 J=1
J=0

(2)

MIT-MANIPAL BE-PHYSICS-QUANTUM MECHANICS-2010-2011 34

Solution (b)

Solution (c)

35
 BONDING IN SOLIDS
A crystalline solid consists of a large number of atoms
arranged in a regular array, forming a periodic structure.

Ionic Solids: These are formed by ionic bonding, due

to electrostatic force between ions.

In NaCl crystal each Na+ion has six nearest-neighbour

Cl–ions, and each Cl– ion has six nearest-neighbour
Na+ions.
Each ion is in the environment of six attractive nearest-
neighboursat a distance r and 12 repulsive next nearest-
neighbours at a distance , and so on.
36
These interactions give rise to a net attractive potential
energy:

ke= electrical constant,

α = dimensionless number called Madelung constant
depends only on the particular crystalline structure of the
solid.

When the constituent ions of a crystal are brought close

together, a repulsive force exists because of electrostatic
forces and the exclusion principle.

37
 BONDING IN SOLIDS
Total potential energy of the crystal:

UTOTAL has a minimum value Uo(= ionic cohesive

energy of the solid) at r = ro(equilibrium separation
distance), given by
Potential energy is minimum at r=r0.

38
 Where m- a small number

The ionic cohesive energy of a solid is the energy

required to separate the solid into a collection of
isolated positive and negative ions.

The atomic cohesive energy of a solid is the energy

required to separate the solid into a collection of
isolated neutral atoms.

39
 BONDING IN SOLIDS

General properties of the ionic crystals:

1.Ionic crystals are hard and stable.
2.They are bad conductors of electricity.
3.They have high melting points.
4.They are transparent in the visible region but
absorb strongly in the infrared region.
5.They are soluble in polar solvents like water.

MIT- MANIPAL 40
Covalent Solids: These are formed by covalent
bonding.

Eg, diamond is a face centered cubic crystal formed by

covalently bonded carbon atoms.

In this each C-atom is bonded to four other C-atoms

(nearest neighbours) at the corners of a regular
tetrahedron. The angle between the bonds is 109.5 .

CRYSTAL STRUCTURE OF DIAMOND,

SHOWING TETRAHEDRAL BONDS
41
ARRANGEMENT.
 BONDING IN SOLIDS

Silicon and germanium crystals have the same diamond

cubic structure. The atomic cohesive energies of
covalent crystals are large.

Hence the covalent crystals are hard and have high

melting point.

They are good electrical insulators.

MIT- MANIPAL 42
 BONDING IN SOLIDS
Metallic Solids: Metallic bonds are weaker
than ionic or covalent bonds. The
valence electrons of a metal-atom are “free”
electrons and they are large in number in
a metallic solid. The metallic structure is a
gas of these “free” electrons surrounding a
lattice of positive ions.
The bonding mechanism in a metal is the attractive
force between the entire collection of positive ions and
the electron gas.
The cohesive energies of the metals are less than
those of ionic or covalent solids. Visible light is
absorbed and re-emitted on the surface of the metal
due to strong interaction between light and “free”
electrons. Metals are ductile and malleable. They are
good conductors of heat and electricity.
43
 BONDING IN SOLIDS
SJ-PROBLEM 43.25: Consider a one-dimensional chain
of alternating positive and negative ions. Show that the
potential energy associated with one of the ions and its
interactions with the rest of this hypothetical crystal is

where the Madelung constant is  = 2 ln2 and r is the

inter-ionic spacing.

Hint: Use the series expansion

MIT- MANIPAL 44
45
 FREE ELECTRON THEORY OF METALS
Free-electron = valence electron = conduction electron.
Metal = gas of free-electrons in a lattice of positive ions.

The free-electrons are free to move through the metal

but are trapped within a three-dimensional box formed
by the metal surfaces.

Therefore, each free-electron is a particle in a box,

which is restricted to quantized energy levels.

Each energy level can have two states one for electron
with spin up & the other with spin down.
Pauli exclusion principle allows the occupation of an
energy state by one electron only.
46
Fermi-Dirac distribution function (fermi-factor),f(E),
gives the probabilitythat a state of a given energy (E) is
occupied by an electron.

Fermi energy (EF) is the most probable, or the average

energy of the electrons across which the energy transitions
occur at temperatures above zero degree absolute.
Or
the energy of the highest occupied level at zero degree
absolute is fermi energy, the energy level is referred to
as fermi level.

47
 f(E)
AT T = 0 K
1.0

AT T > 0 K
0.5
HIGH TEMP

0
E
E
F

At zero T=0 K all states with energy E < EF are

occupied and all states with energy E > EF are vacant.

At T > 0 (ordinary temperature), the probability of electron

occupation by Fermi level (EF) is half.

48
Density of
states
Band is spread over an
•
ENERGY

energy range of few

BANDS
SINGLE ENERGY SPLIT ENERGY (BUNCHES OF N
LEVELS LEVELS ENERGY LEVELS)

electron volts (eV).

•

The no of energy levels in

•

each band is very large and a

volume 1mm3 solid
contains more than a
thousand billion permitted E

energy levels.
E
E

Density of states is the no

•

of allowed energy levels per ISOLATED ATOM SOLID

unit energy interval in the

2 ATOMS
(N ATOMS)
(DIATOMIC MOLECULE)

band associated with the

material of unit volume.
•

The ability of a metal to

•

conduct electricity depends

 FREE ELECTRON THEORY OF METALS
DERIVATION OF DENSITY-OF-STATES FUNCTION:
The quantized energy states of a particle (mass m) in a
one dimensional box of (length L) are

, n = 1, 2, 3, . . .

For a free-electron (mass m) in a metal cube of side L

(three-dimensional box), the quantized energies are

nx, ny, nz = quantum numbers.

50
 FREE ELECTRON THEORY OF METALS
Each allowed energy value is characterized by this set
of quantum numbers (nx, ny, nz- one for each degree of
freedom) and the spin quantum number ms(two values).
Because of the macroscopic size L of the box, the
energy levels for the electrons are very close together.
As a result, the quantum numbers can be treated as
continuous variables.

In a three-dimensional quantum
number space with axis
representing nx, ny, nz, the
allowed energy states can be
represented as dots located at
positive integral values of the
three quantum numbers.
51
 FREE ELECTRON THEORY OF METALS
Energy equation in 3D-box can be written as

This is the equation of a sphere of radius n.

 Thus, the number of allowed
energy states having energies
between E and E+dE is equal to
the number of points in a
spherical shell of radius n and
thickness dn.

nZ The “volume” of this shell

(NUMBER OF STATES FROM E
TO E+dE) is
dn
n G(E) dE = (⅛)(4n2dn)
nY
= (½)n2dn
53
nX
Since all the nx, ny, nz can have positive values only in
an octant of the three-dimensional space. 53
 g(E) IS THE NUMBER OF STATES PER UNIT
VOLUME [V IN NORMAL SPACE] PER UNIT
ENERGY RANGE

Replacing n by,
To consider the spin states, each particle-in-a-box state
should be multiplied by 2.

g(E) is called the density-of-states function.

For a metal in thermal equilibrium, the number of electrons
per unit volume, N(E) dE, that have energy between E and
E+dE is equal to the product of the number of allowed
states g(E) and the probability f(E) that a state is occupied:

i.e N(E) dE= g(E) f(E)dE

EF
The total number of electrons per unit volume:

EF
At T = 0, f(E) = 1 for E < EF and f(E) = 0 for E > EF.

 At T = 0, FREE-ELECTRON
DENSITY IN A
METAL AT ZERO K

FERMIF ENERGY OF A
METAL AT ZERO K

The average energy of a free-electron in a metal at zero K

is

At zero K, all levels below EF are filled with electrons and

all levels above EF are empty. At 300 K, a very small
fraction of the free electrons are excited above EF.
SJ-EXAMPLE 43.4: The Fermi Energy of Gold:
Each atom of gold (Au) contributes one free-electron to
the metal. The concentration of free-electron in gold is
5.90 x 1028 /m3. Compute the Fermi Energy of gold.
Solution:

Answer: EF=8.85 x 10-19 J=5.53 eV

SJ-PROBLEM 43.29: Sodium is a monovalent metal
having a density of 971 kg/m3 and a molar mass of
0.023 kg/mol. Use this information to calculate (a) the
density of charge carriers and (b) the Fermi energy.

Solution (a):
Solution:B

EF=5.05 x 10-19 J=3.15 eV

SJ-PROBLEM 43.31: Calculate the energy of a
conduction electron in silver at 800 K, assuming the
probability of finding an electron in that state is 0.950.
The Fermi energy is 5.48 eV at this temperature.

Solution:

k=1.38 x 10-23
SJ-PROBLEM 43.33: Show that the average kinetic
energy of a conduction electron in a metal at zero K
is
Suggestion: In general the average, the average kinetic
energy is where the
density of particles

Solution: We have
 SJ-PROBLEM 43.35: (a) Consider a system of
electrons confined to a three-dimensional box. Calculate
the ratio of the number of allowed energy levels at
8.50 eV to the number at 7.00 eV. (b) Copper has a
Fermi energy of 7.0 eV at 300 K. Calculate the ratio of
the number of occupied levels at an energy of 8.50 eV
to the number at Fermi energy. Compare your
answer with that obtained in part (a).
Solution:
(a) The density-of-states at energy E .

Hence the ratio required is.

Solution(b):
 BAND THEORY OF SOLIDS
There are two different wave functions and
(for an atom with single s-electron outside of a closed
shell) for which the probability density is the same.
The wave functions of two atoms combine to form a
composite wave function for the two-atom system when
the atoms are close together. In Figure (a), two atoms
with wave functions combine. In Figure (b), two
atoms with wave functions and combine. These
two possible combinations of wave functions
represent two possible states of the two-atom.

system which have slightly different

energies. Thus, each energy level of an
atom splits into two close energy levels
when the wave functions of the two
atoms overlap.
Figure (a) shows the splitting of 1s and 2s levels when
two sodium atoms are brought together.
Figure (b) shows the splitting of 1s and 2s levels into
five levels each when five sodium atoms are brought
together.
Figure (c) shows formation of energy bands (bunches
of closely spaced energy levels) when a large number
of sodium atoms are assembled to form a solid.

ENERGY BANDS OF
SODIUM CRYSTAL

3p
3s
E
2p

2s

1s
Thus, in a crystalline solid there are a large number of
allowed energy bands that arise from the various
atomic energy levels. Forbidden energy gaps occur
between the allowed bands. Some bands may be wide
enough in energy so that there is an overlap between
the adjacent bands. The 1s, 2s, and 2p bands of solid
sodium are filled completely with electrons. Since there
are 2(2l+1) energy states in a

subshell each energy band has ENERGY BANDS OF

2(2l+1)N energy states, SODIUM CRYSTAL
where N = number of atoms in the 3p
crystal. 3s
E
The 3s band (2N states) of solid sodium 2p
has only N electrons and is partially 2s
full; The 3p band and the bands above
1s
this are completely empty.
 ELECTRICAL CONDUCTION IN METALS,
INSULATORS AND SEMICONDUCTORS
Good electrical conductors contain high density of free
charge carriers, and the density of free charge carriers in
insulators is nearly zero. In semiconductors free-charge-
carrier densities are intermediate between those of insulators
and those of conductors.

Metals: Metal (an electrical conductor) has a partially filled

energy band. Highest electron-occupied energy level is the
Fermi-level, at zero K. If a potential difference is applied to
the metal, electrons having energies near the Fermi energy
require only a

small amount of additional energy from

Eg = 0
PARTIALLY FILLED the applied field to reach nearby empty
VB & CB E=EF energy states above the Fermi-level.
E=0
Hence metal is a good electrical
CONDUCTOR conductor.
Insulators: In these the outermost energy bands are filled
valence band and empty conduction band with a large
energy gap (Eg>>kT, kT= thermal energy). The Fermi-level
lies in the energy gap. Thermal energy at room temperature
is not sufficient to excite the electrons from valence-band to
conduction band. Since the free-electron density is nearly
zero, these materials are bad conductors of electricity.
Semiconductors: These have the same type of band
structure as an insulator but the energy gap is much smaller
( 1 eV). At room temperature a small fraction of valence
electrons are thermally excited to conduction band

CONDUCTION BAND
EMPTY CB
Eg EF
Eg EF
FILLED VB VALENCE BAND

INSULATOR SEMICONDUCTOR
At zero K, all electrons in semiconductors are in the valence
band, and no energy is available to excite them across the
energy gap. Thus, semiconductors are poor conductors at
very low temperatures. Because the thermal excitation of
electrons across the narrow gap is more probable at higher
temperatures, the conductivity of semiconductors increases
rapidly with temperature. [The conductivity of a metal
decreases slowly with increasing temperature.]
The charge carriers in a semiconductors are electrons
and holes. When an electron moves from the valence band
into the conduction band, it leaves behind a vacant site,
called a hole (particle with a positive charge +e).
When a conduction electron from a nearby site
transfers into the hole, the hole is said to drift to the
position of the conduction electron. Thus, the hole
migrates opposite to the direction of electron movement.
In an intrinsic semiconductor (pure semiconductor)
there are equal number of conduction electrons and
holes.
In the presence of an
external electric field, the
ELECTRONS
HOLES
holes move in the direction
CONDUCTION
ELECTRONS CONDUCTION of field and the conduction
BAND electrons move opposite to
ENERGY GAP
the direction of the field.
Both these motions
VALENCE BAND correspond to the current in
the same direction.
APPLIED E-FIELD
Doped Semiconductors: Doping is the process of
adding impurities to a semiconductor. By doping both the
band structure of the semiconductor and its resistivity are
modified. If a tetravalent semiconductor (Si or Ge) is doped
with a pentavalent impurity atom (donor atom), four of the
electrons form covalent bonds with atoms of the
semiconductor and one is left over. At zero K, this extra
electron resides in the donor-levels, that lie in the energy
gap, just below the conduction band.
Since the energy Ed between the donor levels and the
bottom of the conduction band is small, at room
temperature, the extra electron is thermally excited to
the conduction band. This type of semiconductors are
called n-type semiconductors because the majority of
charge carriers are electrons (negatively charged).

If a tetravalent semiconductor is doped with a trivalent

impurity atom (acceptor atom), the three electrons form
covalent bonds with neighbouring semiconductor
atoms, leaving an electron deficiency (a hole) at the
site of fourth bond. At zero K, this hole resides in the
acceptor levels that lie in the energy gap just above
the valence band.
Since the energy Ea between the acceptor levels and
the top of the valence band is small, at room
temperature, an electron from the valence band is
thermally excited to the acceptor levels leaving behind
a hole in the valence band. This type of
semiconductors are called p-type semiconductors
because the majority of charge carriers are holes
(positively charged).
The doped semiconductors are called extrinsic
semiconductors.
SJ-PROBLEM 43.37: Light from a hydrogen discharge
tube is incident on a CdS crystal (Eg= 2.42 eV). Which
spectral line from the Balmer series are absorbed and
which are transmitted ?
Solution:

Photons of energy greater than 2.42 eV will be absorbed.

This means wavelength shorter than

All Balmer lines absorbed except the red line (656 nm)
which is transmitted.
VISIBLE HYDROGEN SPECTRUM
BALMER SERIES LINES
H (656.3 nm) H (656.3 nm)
H (656.3 nm) H (656.3 nm)
SJ-PROBLEM 43.39: Most solar radiation has a
wavelength of 1 μm or less. What energy gap should
the material in solar cell have in order to absorb this
radiation ? Is silicon (Eg= 1.14 eV) appropriate ?
solution:

Thus, the energy gap for the collector material should be

Eg ≤ 1.24 eV. Since Si has an energy gap Eg ≈ 1.14 eV, it will
absorb radiation of this energy and greater. Therefore, Si is
acceptable as a material for a solar collector.
 SEMICONDUCTOR DEVICES
The Junction Diode:
pn-junction is formed when a
p-type semiconductor is joined
to an n-type semiconductor.
A pn-junction has
three distinct regions: a p-
region, an n-region, and a
depletion region at the junction
[Figure (a)]. The depletion
region has no movable
charges (conduction electrons
and holes) because the
conduction electrons on the n- ∆
side have crossed the junction
due to diffusion and ∆
neutralized the holes on the
p-side.
Because of the fixed ion cores in the depletion region,
an electric field exists [Figure (b)], due to which there
is a potential difference
∆Vo across the junction
[Figure (c)].
In the forward bias, the p-
side of the junction is CHARACTERISTIC
CURVE OF A
made positive with respect to pn-JUNCTION
the n-side, by application of
an external voltage ΔV.
Then the internal potential
difference ΔVo across the
junction decreases. This
gives rise to a current I
which increases exponentially ∆
with the increase in
forward bias ΔV.
In the reverse bias, the p-side of the junction is made
negative with respect to the n-side, by application of a
negative voltage ΔV.

Then the internal potential difference ΔVo across the

junction increases. This gives rise to a reverse current
that quickly reaches a saturation value Io(reverse
saturation current). The current in an ideal diode
under the biasing voltage ΔV at temperature T is
SJ-PROBLEM 43.42: For what value of the bias
voltage in the
diode-current equation does

(a) I = 9.00 Io? (b) I = –0.900 Io? Assume T= 300 K.

solution:
SJ-PROBLEM 43.44: The current in a diode under
forward bias of 100 mV is 200 mA at a temperature of
300 K. What is the current in the diode if it is under
reverse bias of 100 mV ?
Solution:
Light-Emitting and Light-Absorbing Diodes:
An electron excited electrically into the conduction
band (injected into a p-region of a LED [LIGHT-EMITTING
DIODE]) can easily recombine with a hole (Figure a).
Then, a photon of energy Eg is emitted.

This is the principle of light-emission from an LED or

a semiconductor laser. Conversely, an electron in the
valence band may absorb an incoming photon of light
and be promoted to the conduction band, leaving a
hole behind (Figure b). This absorbed energy can be
used to operate an electrical circuit (PHOTOVOLTAIC SOLAR CELL).
SJ-EXAMPLE 43.6: Where’s the Remote ?
Estimate the band gap energy of the semiconductor in
the infrared LED (wavelength = 1.0 μm) of a typical TV-
remote control.

Solution:

The energy of the photons given by E=hc/λ therefore the

energy of the photons from the remote control is

E=hc/λ= 1.2 eV
The Transistor:
A junction transistor is a semiconducting material in
which a very narrow n-region is sandwiched between
two p-regions or a very narrow p-region is sandwiched
between two n-regions. It is formed by two pn-
junctions.
A MOSFET is metal-oxide-semiconductor field-
effect transistor (Figure a). In this there are
three metal connections to the transistor:
source, drain, and gate. The source and drain
are connected to n-type semiconductor regions.
These regions are connected by a narrow
channel of n-type material [n-CHANNEL].
The source and drain regions
and the n-channel are
embedded in a p-type
substrate material.
This forms a depletion region along the bottom of
the n-channel. The gate is separated from the n-
channel by a layer of insulating silicon dioxide.
Thus it does not make electrical contact with the
rest of the semiconducting material.
If a voltage ΔVSD is applied across the source and drain
[Figure b], the electrons flow
through the upper region of the n-
channel, because the lower part of the
n-channel is depleted of charge carriers.
Now, if a second voltage ΔVSG is
applied across the source and gate with
the positive potential on the
gate [Figure c], the depletion region in
the n-channel become narrower and
hence the source-drain current increases.
If a varying voltage is applied to the gate, the
source-drain current also varies. A small
variation in gate voltage ΔVSG results in a large
variation in source-drain current, and a correspondingly
large output-voltage across the resistor in Figure c.

Therefore, the MOSFET acts as a voltage amplifier.

If a negative potential is applied to the gate, the n-
channel decreases in size when ΔVSG increases. This
reduces the source-drain current and stops the current
when ΔVSG is large. Thus MOSFET can be used as
on-off switch by changing the polarity of ΔVSG .
The Integrated Circuit: An integrated circuit (IC) is a
collection of interconnected transistors, diodes, resistors,
and capacitors fabricated on a single piece of silicon
known as a chip.
ICs were invented partly to solve the interconnection
problem spawned by the transistor. In addition to
solving the interconnection problem, ICs possess the
advantages of miniaturization and fast response.
R SUPERCONDUCTIVITY
Superconductors are the materials whose
electrical resistance (R) decreases to zero
below a certain temperature TC called the
0 critical temperature (4.2 K for Hg).
T
TC
Meissner effect is the exclusion
of magnetic flux from the interior
SUPERCONDUCTING
ROD IN MAGBETIC

of superconductors when their

temperature is decreased below
FIELD B

the critical temperature.

∆V  E
∆V = potential difference across the material
I = current in the material
= electric field in the material
Since R = 0 in the superconductor below TC, ∆V = 0
or E=0

Faraday,s law of induction:

i.e., the line integral of the electric field around any

closed loop is equal the negative rate of change in the
magnetic flux  B through the loop.
Since = 0 in the super conductor (below TC)

i.e., the magnetic flux in the superconductor

cannot change.  magnetic field, B = B/A =
constant inside the superconductor. From
Meissner effect, one can write, B= 0 or B=
0 inside a superconductor, below TC.  the
If a magnetic field B is applied on the superconductor and
its value is increased, the superconductivity disappears when
B > BC= critical magnetic field.
A diamagnet has a negative magnetic susceptibility. It is
repelled by a magnetic field. Because of this a small
permanent magnet can be made to float (levitate) in air,
above a superconductor (below TC).
A superconductor expels magnetic flux (Meissner effect) by
forming surface currents. These surface currents induced in
the superconductor produce a magnetic field that exactly
cancels the externally applied magnetic field inside the
superconductor.
MAGNETIC 91
 BCS theory of superconductivity in metals:
According to this theory, two electrons can interact
via distortions in the array of lattice ions so that
there is a net attractive force between the
electrons. As a result, the two electrons, are bound
into an entity called a Cooper pair. The Cooper
pair behaves like a boson (= particle with integral
spin that do not obey the Pauli exclusion principle).
At very low temperature, it is possible for all
bosons in a collection of such particles to be in the
lowest quantum state. As a result, the entire
collection of Cooper pairs in the metal is described
Under the action of an applied electric field, the Cooper
pairs experience an electric force and move through the
metal. A random scattering event of a Cooper pair from
a lattice ion would represent resistance to the electric
current. Such a collision would change the energy of the
Cooper pair because some energy would be transferred to
the lattice ion. But there are no available energy levels
below that of the Cooper pair (it is already in the lowest
state) and none available above, because of the energy
gap. As a result, collisions do not occur and there is no
resistance to the movement of Cooper pairs.
SJ-PROBLEM 43.46: A thin rod of superconducting
material 2.50 cm long is placed into a 0.540-T magnetic
field with its cylindrical axis along the magnetic field
lines. (a) Sketch the directions of the applied field and
the induced surface current. (b) Find the magnitude of
the surface current on the curved surface of the rod.
Solution:
SJ-PROBLEM 43.47: Determine the current generated
in a superconducting ring of niobium metal 2.00 cm in
diameter when a 0.0200-T magnetic field directed
perpendicular to the ring is suddenly decreased to
zero. The inductance of the ring is 3.10 x 10–8 H.
Solution:

By Faraday’s law
QUESTIONS – MOLECULES AND SOLIDS
[MARKS]
1.Sketch schematically the plot of potential energy and
its components as a function of internuclear
separation distance for a system of two atoms. [2]
2.Explain briefly (a) ionic bonding, (b) covalent bonding,
(c) van der Walls bonding, (d) hydrogen bonding.
[2EACH]
3.Obtain an expression for rotational energy of a
diatomic molecule. Sketch schematically these
rotational energy levels. [5]
4.Obtain expressions for rotational transition photon
energies and frequencies. [2]
5.Obtain an expression for vibrational energy of a
diatomic molecule. Sketch schematically these
vibrational energy levels. Obtain expression for
vibrational transition photon energies. [5]
96
QUESTIONS – MOLECULES AND SOLIDS
[MARKS]

6.Write expression for total energy (vibrational and

rotational) of a molecule. Sketch schematically these
energy levels of a diatomic molecule for the lowest
two vibrational energy values, indicating the possible
transitions. Write the expressions for the energy of
the photon in the molecular energy transitions.
Write the expression for the frequency separation of
adjacent spectral lines. [5]
7.Explain the expression for the total potential energy
of a crystal. Sketch schematically the plot of the
same. [3]
8.Define (a) ionic cohesive energy (b) atomic cohesive
energy, of a solid. [1EACH]

97
QUESTIONS – MOLECULES AND SOLIDS
[MARKS]
9.Write the expression for Fermi-Dirac distribution
function. Sketch schematically the plots of this
function for zero K and for temperature > zero K.
[2]
10.Derive the density-of-states function. [6]
11.
12.Assuming the Fermi-Dirac distribution function and
the density-of-states function, obtain (a)
an expression for the density of free-electrons
(MASSm) in a metal with Fermi energy EF, at zero K
(b) an expression for Fermi energy EF in a metal in
terms of density (ne) of free electrons (MASS m), at
zero K. [5]

98
QUESTIONS – MOLECULES AND SOLIDS
[MARKS]
12.Explain briefly the energy band theory of solids.
[6]
13.Explain the classification of solids regarding the
electrical properties, based on their energy band
diagram. [5]
14.Indicate the position of (a) Fermi-level (b) donor
levels (c) acceptor levels, in the energy band
diagram of a semiconductor. [2]
15.Explain the terms: Conductor, insulator,
semiconductor, intrinsic semiconductor, extrinsic
semiconductor, n-type semiconductor, p-type
semiconductor, valence band, conduction band,
donor levels, acceptor levels. [1EACH]

99
QUESTIONS – MOLECULES AND SOLIDS
[MARKS]

16.Write a note on junction diode. [5]

17.Write a note on light emitting and light absorbing
diodes. [4]
18.Write a note on MOSFET. [6]
19.Sketch schematically the plot of resistance of a
superconducting material vs temperature, near the
critical temperature. [1]
20.Explain Meissner effect. [2]
21.Give a brief account of superconductivity. [5]
22.Explain briefly the BCS theory of superconductivity in
metals. [4]

100