Chapter 43

Molecules and Solids

Molecular Bonds –
Introduction
 The bonding mechanisms in a molecule
are fundamentally due to electric forces
 The forces are related to a potential
energy function
 A stable molecule would be expected at
a configuration for which the potential
energy function has its minimum value
Molecular Bonds – Feature 1
 The force between atoms is repulsive at
very small separation distances
 This repulsion is partially electrostatic and
partially due to the exclusion principle
 Due to the exclusion principle, some
electrons in overlapping shells are forced
into higher energy states
 The energy of the system increases as if a
repulsive force existed between the atoms
Molecular Bonds – Feature 2
 The force between the atoms is
attractive at larger distances
 The attractive force (for many molecules) is
due to the dipole-dipole interaction
between charge distributions within the
atoms of the molecules
 The electric fields of two dipoles will
interact, resulting in a force between the
dipoles
Potential Energy Function
 The potential energy for a system of two
atoms can be expressed in the form
A B
U (r )   n  m
r r
 r is the internuclear separation distance
 m and n are small integers
 A is associated with the attractive force
 B is associated with the repulsive force
Potential Energy Function,
Graph
 At large separations,
the slope of the curve is
positive
 Corresponds to a net
attractive force
 At the equilibrium
separation distance, the
attractive and repulsive
forces just balance
 At this point the potential
energy is a minimum
 The slope is zero
Molecular Bonds – Types
 Simplified models of molecular bonding
include
 Ionic
 Covalent
 van der Waals
 Hydrogen
Ionic Bonding
 Ionic bonding occurs when two atoms
combine in such a way that one or more
outer electrons are transferred from one
atom to the other
 Ionic bonds are fundamentally caused
by the Coulomb attraction between
oppositely charged ions
Ionic Bonding, cont.
 When an electron makes a transition
from the E = 0 to a negative energy
state, energy is released
 The amount of this energy is called the
electron affinity of the atom
 The dissociation energy is the amount
of energy needed to break the
molecular bonds and produce neutral
atoms
 Ionic Bonding, NaCl Example

 The graph shows the total energy of the molecule

vs the internuclear distance
 The minimum energy is at the equilibrium
separation distance
Ionic Bonding,final
 The energy of the molecule is lower
than the energy of the system of two
neutral atoms
 It is said that it is energetically
favorable for the molecule to form
 The system of two atoms can reduce its
energy by transferring energy out of the
system and forming a molecule
Covalent Bonding
 A covalent bond between two atoms is
one in which electrons supplied by
either one or both atoms are shared by
the two atoms
 Covalent bonds can be described in
terms of atomic wave functions
 The example will be two hydrogen
atoms forming H2
Wave Function – Two Atoms
Far Apart
 Each atom has a
wave function
1
ψ1s (r )  e  r ao
πao3
 There is little overlap
between the wave
functions of the two
atoms
Wave Function – Molecule
 The two atoms are
brought close together
 The wave functions
overlap and form the
compound wave shown
 The probability
amplitude is larger
between the atoms than
on either side
Active Figure 43.3

(SLIDESHOW MODE ONLY)

Covalent Bonding, Final
 The probability is higher that the electrons
associated with the atoms will be located
between them
 This can be modeled as if there were a fixed
negative charge between the atoms, exerting
attractive Coulomb forces on both nuclei
 The result is an overall attractive force
between the atoms, resulting in the covalent
bond
Van der Waals Bonding
 Two neutral molecules are attracted to each
other by weak electrostatic forces called van
der Waals forces
 Atoms that do not form ionic or covalent bonds are
also attracted to each other by van der Waals
forces
 The van der Waals force is due to the fact
that the molecule has a charge distribution
with positive and negative centers at different
positions in the molecule
Van der Waals Bonding, cont.
 As a result of this charge distribution,
the molecule may act as an electric
dipole
 Because of the dipole electric fields, two
molecules can interact such that there
is an attractive force between them
 Remember, this occurs even though the
molecules are electrically neutral
Types of Van der Waals
Forces
 Dipole-dipole force
 An interaction between two molecules each
having a permanent electric dipole moment
 Dipole-induced dipole force
 A polar molecule having a permanent
dipole moment induces a dipole moment in
a nonpolar molecule
Types of Van der Waals
Forces, cont.
 Dispersion force
 An attractive force occurs between two nonpolar
molecules
 The interaction results from the fact that, although
the average dipole moment of a nonpolar
molecule is zero, the average of the square of the
dipole moment is nonzero because of charge
fluctuations
 The two nonpolar molecules tend to have dipole
moments that are correlated in time so as to
produce van der Waals forces
Hydrogen Bonding
 In addition to covalent bonds, a
hydrogen atom in a molecule can also
form a hydrogen bond
 Using water (H2O) as an example
 There are two covalent bonds in the
molecule
 The electrons from the hydrogen atoms are
more likely to be found near the oxygen
atom than the hydrogen atoms
Hydrogen Bonding –
H2O Example, cont.
 This leaves essentially bare protons at
the positions of the hydrogen atoms
 The negative end of another molecule
can come very close to the proton
 This bond is strong enough to form a
solid crystalline structure
Hydrogen Bonding, Final
 The hydrogen bond
is relatively weak
compared with other
electrical bonds
 Hydrogen bonding is
a critical mechanism
for the linking of
biological molecules
and polymers
 DNA is an example
Energy States of Molecules
 The energy of a molecule (assume one
in a gaseous phase) can be divided into
four categories
 Electronic energy

Due to the interactions between the molecule’s
electrons and nuclei
 Translational energy

Due to the motion of the molecule’s center of
mass through space
 Energy States of Molecules, 2
 Categories, cont.
 Rotational energy
 Due to the rotation of the molecule about its
center of mass
 Vibrational energy
 Due to the vibration of the molecule’s constituent
atoms
 The total energy of the molecule is the
sum of the energies in these categories:
 E = Eel + Etrans + Erot + Evib
Spectra of Molecules
 The translational energy is unrelated to
internal structure and therefore
unimportant to the interpretation of the
molecule’s spectrum
 By analyzing its rotational and
vibrational energy states, significant
information about molecular spectra
can be found
Rotational Motion of
Molecules
 A diatomic model will be
used, but the same
ideas can be extended
to polyatomic molecules
 A diatomic molecule
aligned along an x axis
has only two rotational
degrees of freedom
 Corresponding to
rotations about the y and
x axes
Rotational Motion of
Molecules, Energy
 The rotational energy is given by
1
rot 
2
Eω I
2
 I is the moment of inertia of the molecule
 m1 m2  2
I   rμr
2

 m1  m2 
 µ is called the reduced mass of the molecule
Rotational Motion of Molecules,
Angular Momentum
 Classically, the value of the molecule’s
angular momentum can have any value
L = Iω
 Quantum mechanics restricts the values
of the angular momentum to
L  J  J  1 h J  0 , 1, 2,K
 J is an integer called the rotational
quantum number
Rotational Kinetic Energy of
Molecules, Allowed Levels
 The allowed values are
h2
Erot  J  J  1 J  0 , 1, 2,K
2I
 The rotational kinetic energy is
quantized and depends on its moment
of inertia
 As J increases, the states become
farther apart
 Allowed Levels, cont.
 For most molecules,
transitions result in radiation
that is in the microwave
region
 Allowed transitions are given
by the condition
h2 h2
Erot  J  2
J
I 4π I
J  1, 2, 3 ,K
 J is the number of the higher
state
Active Figure 43.5

(SLIDESHOW MODE ONLY)

Sample Transitions –
CO Example
Vibrational Motion of
Molecules
 A molecule can be
considered to be a
flexible structure
where the atoms are
bonded by “effective
springs”
 Therefore, the
molecule can be
modeled as a simple
harmonic oscillator
Vibrational Motion of
Molecules, Potential Energy
 A plot of the
potential energy
function
 ro is the equilibrium
atomic separation
 For separations
close to ro, the
shape closely
resembles a
parabola
Vibrational Energy
 Classical mechanics describes the frequency
of vibration of a simple harmonic oscillator
 Quantum mechanics predicts that a molecule
will vibrate in quantized states
 The vibrational and quantized vibrational
energy can be altered if the molecule
acquires energy of the proper value to cause
a transition between quantized states
Vibrational Energy, cont.
 The allowed vibrational energies are
 1
Evib   v  h ƒ v  0 , 1, 2,K
 2
 v is an integer called the vibrational quantum
number
 When v = 0, the molecule’s ground state
energy is ½hƒ
 The accompanying vibration is always present,
even if the molecule is not excited
Vibrational Energy, Final
 The allowed vibrational
energies can be expressed
as
 1 h k
Evib   v  
 2  2π μ
v  0 , 1, 2,K
 Allowed transitions are
Δv = ±1
 The energy between
states is ΔEvib = hƒ
Some Values for Diatomic
Molecules
Molecular Spectra
 In general, a molecule vibrates and
rotates simultaneously
 To a first approximation, these motions
are independent of each other
 The total energy is the sum of the
energies for these two motions:
 1 h2
E   v  h ƒ  J  J  1
 2 2I
 Molecular Energy-Level
Diagram
 For each allowed state of v,
there is a complete set of
levels corresponding to the
allowed values of J
 The energy separation
between successive
rotational levels is much
smaller than between
successive vibrational levels
 Most molecules at ordinary
temperatures vibrate at v = 0
level
 Molecular Absorption
Spectrum

 The spectrum consists of two groups of lines

 One group to the right of center satisfying the selection rules
ΔJ = +1 and Δv = +1
 The other group to the left of center satisfying the selection
rules ΔJ = -1 and Δv = +1
 Adjacent lines are separated by /2πI
Active Figure 43.8

(SLIDESHOW MODE ONLY)

 Absorption Spectrum of HCl

 It fits the predicted pattern very well

 A peculiarity shows, each line is split into a doublet
 Two chlorine isotopes were present in the same

sample
 Because of their different masses, different I’s are

present in the sample

Intensity of Spectral Lines
 The intensity is determined by the
product of two functions of J
 The first function is the number of available
states for a given value of J
 There are 2J + 1 states available
 The second function is the Boltzmann
factor
 h2J (J 1)/(2 I kBT )

n  noe
Intensity of Spectral Lines,
cont
 Taking into account both factors by
multiplying them,
I   2J  1 e  h J (J 1)/(2 I k T )
2
B

 The 2J + 1 term increases with J

 The exponential term decreases
 This is in good agreement with the
observed envelope of the spectral lines
Bonding in Solids
 Bonds in solids can be of the following
types
 Ionic
 Covalent
 Metallic
Ionic Bonds in Solids
 The dominant interaction between ions
is through the Coulomb force
 Many crystals are formed by ionic
bonding
 Multiple interactions occur among
nearest-neighbor atoms
Ionic Bonds in Solids, 2
 The net effect of all the interactions is a
negative electric potential energy
e2
attractive  
Uαk e
r
 is a dimensionless number known as the
Madelung constant
 The value of depends only on the
crystalline structure of the solid
 Ionic Bonds, NaCl Example

 The crystalline structure is shown (a)

 Each positive sodium ion is surrounded by six negative
chlorine ions (b)
 Each chlorine ion is surrounded by six sodium ions (c)
 = 1.747 6 for the NaCl structure
Total Energy in a
Crystalline Solid
 As the constituent ions of a crystal are
brought close together, a repulsive
force exists
 The potential energy term B/rm accounts
for this repulsive force
 This repulsive force is a result of
electrostatic forces and the exclusion
principle
Total Energy in a Crystalline
Solid, cont
 The total potential energy
of the crystal is
e2 B
Utotal = − αk e + m
r r
 The minimum value, Uo, is
called the ionic cohesive
energy of the solid
 It represents the energy
needed to separate the solid
into a collection of isolated
positive and negative ions
Properties of Ionic Crystals
 They form relatively stable, hard
crystals
 They are poor electrical conductors
 They contain no free electrons
 Each electron is bound tightly to one of the
ions
 They have high melting points
More Properties of Ionic
Crystals
 They are transparent to visible radiation, but
absorb strongly in the infrared region
 The shells formed by the electrons are so tightly
bound that visible light does not possess sufficient
energy to promote electrons to the next allowed
shell
 Infrared is absorbed strongly because the
vibrations of the ions have natural resonant
frequencies in the low-energy infrared region
Final Properties of Ionic
Crystals
 Many are quite soluble in polar liquids
 Water is an example of a polar liquid
 The polar solvent molecules exert an
attractive electric force on the charged ions
 This breaks the ionic bonds and dissolves
the solid
Properties of Solids with
Covalent Bonds
 Properties include
 Usually very hard
 Due to the large atomic cohesive energies
 High bond energies
 High melting points
 Good electrical conductors
Cohesive Energies for Some
Covalent Solids
 Covalent Bond Example –
Diamond

 Each carbon atom in a diamond crystal is

covalently bonded to four other carbon atoms
 This forms a tetrahedral structure
Another Carbon Example --
Buckyballs
 Carbon can form
many different
structures
 The large hollow
structure is called
buckminsterfullerene
 Also known as a
“buckyball”
Metallic Solids
 Metallic bonds are generally weaker
than ionic or covalent bonds
 The outer electrons in the atoms of a
metal are relatively free to move
through the material
 The number of such mobile electrons in
a metal is large
 Metallic Solids, cont.
 The metallic structure can
be viewed as a “sea” or
“gas” of nearly free
electrons surrounding a
lattice of positive ions
 The bonding mechanism
is the attractive force
between the entire
collection of positive ions
and the electron gas
Properties of Metallic Solids
 Light interacts strongly with the free
electrons in metals
 Visible light is absorbed and re-emitted
quite close to the surface
 This accounts for the shiny nature of metal
surfaces
 High electrical conductivity
More Properties of Metallic
Solids
 The metallic bond is nondirectional
 This allows many different types of metal
atoms to be dissolved in a host metal in
varying amounts
 The resulting solid solutions, or alloys, may
be designed to have particular properties
 Metals tend to bend when stretched
 Due to the bonding being between all of
the electrons and all of the positive ions
Free-Electron Theory of
Metals
 The quantum-based free-electron theory of
electrical conduction in metals takes into
account the wave nature of the electrons
 The model is that the outer-shell electrons
are free to move through the metal, but are
trapped within a three-dimensional box
formed by the metal surfaces
 Each electron can be represented as a
particle in a box
Fermi-Dirac Distribution
Function
 Applying statistical physics to a
collection of particles can relate
microscopic properties to macroscopic
properties
 For electrons, quantum statistics
requires that each state of the system
can be occupied by only two electrons
Fermi-Dirac Distribution
Function, cont.
 The probability that a particular state
having energy E is occupied by one of
the electrons in a solid is given by
1
ƒ( E )  (E EF ) kBT
e 1
 ƒ(E) is called the Fermi-Dirac
distribution function
 EF is called the Fermi energy
Fermi-Dirac Distribution
Function at T = 0
 At T = 0, all states
having energies less
than the Fermi
energy are occupied
 All states having
energies greater
than the Fermi
energy are vacant
Fermi-Dirac Distribution
Function at T > 0
 As T increases, the
distribution rounds
off slightly
 States near and
below EF lose
population
 States near and
above EF gain
population
Active Figure 43.15

(SLIDESHOW MODE ONLY)

Electrons as a Particle in a
Three-Dimensional Box
 The energy levels for the electrons are
very close together
 The density-of-states function gives
the number of allowed states per unit
volume that have energies between E
and dE:
8 2πme3 2 E 1 2dE
g (E )dE 
h3 e(E EF ) kBT  1
Fermi Energy at T = 0 K
 The Fermi energy at T = 0 K is
2 23
h  3ne 
EF (0)   
2mπ
e  8 
 The order of magnitude of the Fermi
energy for metals is about 5 eV
 The average energy of a free electron in
a metal at 0 K is Eav = (3/5) EF
Fermi Energies for Some
Metals
Wave Functions of Solids
 To make the model of a metal more
complete, the contributions of the
parent atoms that form the crystal must
be incorporated
 Two wave functions are valid for an
atom with atomic number A and a
single s electron outside a closed shell:
ψs (r )   Aƒ(r )e  Zr nao ψs (r )   Aƒ(r )e  Zr nao
 Combined Wave Functions
 The wave functions
can combine in the
various ways shown

s
-
+ s
-
is equivalent to
s
+
+ s
+

 These two possible

combinations of wave
functions represent
two possible states of
the two-atom system
Splitting of Energy Levels
 The states are split into
two energy levels due to
the two ways of combining
the wave functions
 The energy difference is
relatively small, so the two
states are close together
on an energy scale
 For large values of r, the
electron clouds do not
overlap and there is no
splitting of the energy
level
Splitting of Energy
Levels, cont.
 As the number of
atoms increases,
the number of
combinations in
which the wave
functions combine
increases
 Each combination
corresponds to a
different energy
level
Splitting of Energy
Levels, final
 When this splitting is
extended to the large
number of atoms
present in a solid, there
is a large number of
levels of varying energy
 These levels are so
closely spaced they can
be thought of as a band
of energy levels
Energy Bands in a Crystal
 In general, a crystalline solid
will have a large number of
allowed energy bands
 The white areas represent
energy gaps, corresponding
to forbidden energies
 Some bands exhibit an
overlap
 Blue represents filled bands
and gold represents empty
bands in this example of
sodium
Electrical Conduction –
Classes of Materials
 Good electrical conductors contain a high
density of free charge carriers
 The density of charge carriers in an insulator
is nearly zero
 Semiconductors are materials with a charge
density between those of insulators and
conductors
 These classes can be discussed in terms of a
model based on energy bands
Metals
 To be a good conductor, the charge carriers
in a material must be free to move in
response to an electric field
 We will consider electrons as the charge carriers
 The motion of electrons in response to an
electric field represents an increase in the
energy of the system
 When an electric field is applied to a
conductor, the electrons move up to an
available higher energy state
 Metals – Energy Bands
 At T = 0, the Fermi energy
lies in the middle of the band
 All levels below EF are filled
and those above are empty
 If a potential difference is
applied to the metal,
electrons having energies
near EF require only a small
amount of additional energy
from the applied field to
reach nearby higher energy
levels
Metals As Good Conductors
 The electrons in a metal experiencing
only a small applied electric field are
free to move because there are many
empty levels available close to the
occupied energy level
 This shows that metals are good
conductors
Insulators
 There are no available states that lie close in
energy into which electrons can move upward
in response to an electric field
 Although an insulator has many vacant states
in the conduction band, these states are
separated from the filled band by a large
energy gap
 Only a few electrons can occupy the higher
states, so the overall electrical conductivity is
very small
Insulator – Energy Bands
 The valence band is
filled and the conduction
band is empty at T = 0
 The Fermi energy lies
somewhere in the
energy gap
 At room temperature,
very few electrons
would be thermally
excited into the
conduction band
Semiconductors
 The band structure
of a semiconductor
is like that of an
insulator with a
smaller energy gap
 Typical energy gap
values are shown in
the table
 Semiconductors –
Energy Bands
 Appreciable numbers
of electrons are
thermally excited into
the conduction band
 A small applied
potential difference can
easily raise the energy
of the electrons into the
conduction band
Semiconductors –
Movement of Charges
 Charge carriers in a
semiconductor can
be positive,
negative, or both
 When an electron
moves into the
conduction band, it
leaves behind a
vacant site, called a
hole
Semiconductors –
Movement of Charges, cont.
 The holes act as charge carriers
 Electrons can transfer into a hole, leaving
another hole at its original site
 The net effect can be viewed as the
holes migrating through the material in
the direction opposite the direction of
the electrons
 The hole behaves as if it were a particle
with charge +e
Intrinsic Semiconductors
 A pure semiconductor material
containing only one element is called an
intrinsic semiconductor
 It will have equal numbers of conduction
electrons and holes
 Such combinations of charges are called
electron-hole pairs
Doped Semiconductors
 Impurities can be added to a
semiconductor
 This process is called doping
 Doping
 Modifies the band structure of the
semiconductor
 Modifies its resistivity
 Can be used to control the conductivity of
the semiconductor
n-Type Semiconductors
 An impurity can add
an electron to the
structure
 This impurity would be
referred to as a donor
atom
 Semiconductors
doped with donor
atoms are called n-
type semiconductors
n-Type Semiconductors,
Energy Levels
 The energy level of
the extra electron is
just below the
conduction band
 The electron of the
donor atom can
move into the
conduction band as
a result of a small
amount of energy
p-Type Semiconductors
 An impurity can add a hole
to the structure
 This is an electron
deficiency
 This impurity would be
referred to as a acceptor
atom
 Semiconductors doped
with acceptor atoms are
called p-type
semiconductors
 p-Type Semiconductors,
Energy Levels
 The energy level of the
hole is just above the
valence band
 An electron from the
valence band can fill the
hole with an addition of a
small amount of energy
 A hole is left behind in
the valance band
 This hole can carry
current in the presence of
an electric field
Extrinsic Semiconductors
 When conduction in a
semiconductor is the result of
acceptor or donor impurities, the
material is called an extrinsic
semiconductor
 Doping densities range from 1013 to
1019 cm-3
Semiconductor Devices
 Many electronic devices are based on
semiconductors
 These devices include
 Junction diode
 Light-emitting and light-absorbing diodes
 Transistor
 Integrated Circuit
The Junction Diode
 A p-type semiconductor is joined to an
n-type
 This forms a p-n junction
 A junction diode is a device based on
a single p-n junction
 The role of the diode is to pass current
in one direction, but not the other
 The Junction Diode, 2
 The junction has three
distinct regions
 a p region
 an n region
 a depletion region
 The depletion region is
caused by the diffusion of
electrons to fill holes
 This can be modeled as if
the holes being filled were
diffusing to the n region
The Junction Diode, 3
 Because the two sides of the depletion
region each carry a net charge, an
internal electric field exists in the
depletion region
 This internal field creates an internal
potential difference that prevents further
diffusion and ensures zero current in
the junction when no potential
difference is applied
Junction Diode, Biasing
 A diode is forward biased when the p side is
connected to the positive terminal of a battery
 This decreases the internal potential difference
which results in a current that increases
exponentially
 A diode is reverse biased when the n side is
connected to the positive terminal of a battery
 This increases the internal potential difference and
results in a very small current that quickly reaches
a saturation value
Junction Diode:
I-∆V Characteristics
 LEDs and Light Absorption

 Light emission and absorption in semiconductors is

similar to that in gaseous atoms, with the energy bands of
the semiconductor taken into account
 An electron in the conduction band can recombine with a
hole in the valance band and emit a photon
 An electron in the valance band can absorb a photon and
be promoted to the conduction band, leaving behind a
hole
Transistors
 A transistor is formed from two p-n
junctions
 A narrow n region sandwiched between
two p regions or a narrow p region between
two n regions
 The transistor can be used as
 An amplifier
 A switch
Integrated Circuits
 An integrated circuit is a collection of
interconnected transistors, diodes,
resistors and capacitors fabricated on a
single piece of silicon known as a chip
 Integrated circuits
 Solved the interconnectedness problem
posed by transistors
 Possess the advantages of miniaturization
and fast response
Superconductivity
 A superconductor expels magnetic
fields from its interior by forming surface
currents
 Surface currents induced on the
superconductor’s surface produce a
magnetic field that exactly cancels the
externally applied field
Superconductivity and
Cooper Pairs
 Two electrons are bound into a Cooper pair
when they interact via distortions in the array
of lattice atoms so that there is a net
attractive force between them
 Cooper pairs act like bosons and do not obey
the exclusion principle
 The entire collection of Cooper pairs in a
metal can be described by a single wave
function
Superconductivity, cont.
 Under the action of an applied electric field,
the Cooper pairs experience an electric force
and move through the metal
 There is no resistance to the movement of
the Cooper pairs
 They are in the lowest possible energy state
 There are no energy states above that of the
Cooper pairs because of the energy gap
 Superconductivity -
Critical Temperatures
 A new family of
compounds was found that
was superconducting at
“high” temperatures
 The critical temperature is
the temperature at which
the electrical resistance of
the material decreases to
virtually zero
 Critical temperatures for
some materials are shown