Crystal Binding

4 basis categories
Molecular Bonds – Introduction
• To understand the crystal binding, one should
understand how molecules bind together
• 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
Features of Molecular Bonds
• The force between atoms is repulsive at very small
separation distances
 O This repulsion is partially electrostatic and partially due to the
exclusion principle
 O Due to the exclusion principle, some electrons in overlapping
shells are forced into higher energy states
 O The energy of the system increases as if a repulsive force existed
between the atoms
• The force between the atoms is attractive at larger
distances (e.g. due to shifted charge distribution,
induced dipole-dipole interaction)
Potential Energy Function
•The potential energy for a system of two
atoms can be expressed in the form

r is the internuclear separation distance

O m and n are small integers (usually)
O A is associated with the attractive force
O B is associated with the repulsive force
Graph – U(r)

• At large separations, the

slope of the curve is positive
O Corresponds to a net
attractive force (F = dU/dr)
• At the equilibrium separation
distance, the attractive and
repulsive forces just balance
O At this point the potential energy
is a minimum
O The slope is zero (F=0)
Molecular Bonds – Types
 •Simplified models of molecular bonding include
 OIonic
 OCovalent
 Ovan der Waals
 OHydrogen
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 (e.g. Na+ Cl )
Ionic Bonding, cont.
• The energy required to remove an electron from
an atom is called Ionization Energy. (Na+)
• The amount of energy gained by adding an
electron (from far away E=0) to an atom (E<0) is
called the Electron Affinity of the atom. (Cl)
• The Binding Energy (or 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
Binding energy = 4.2 eV
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
OThe 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 (bonding energy 4.48 eV)
Covalent bonds

Bonding can occur

without outright
removal or addition
of an electron. In
these types of
bonds, the
connection occurs
through orbital
overlap.
Wave Function
– Two Atoms Far Apart
• Each atom has a wave
function (1s1)
1
ψ1s (r )  e r ao

πao3

• There is little overlap

between the wave
functions of the two atoms
when they are far away
from each other
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
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 (typically 0.1 eV)
OAtoms 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
ORemember, this occurs even though the molecules
are electrically neutral
Oe.g.Liquid nitrogen molecules N2
Types of Van der Waals Forces
 •Dipole-dipole force
 OAn interaction between two molecules each having a
permanent electric dipole moment
 •Dipole-induced dipole force
 OA polar molecule having a permanent dipole moment
induces a dipole moment in a nonpolar molecule
Types of Van der Waals Forces, cont.

•Dispersion force
O An attractive force occurs between two nonpolar molecules
O 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
O 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 (weak ≤
0.5 eV)
 •Using water (H2O) as an example
 OThere are two covalent bonds in the molecule
 OThe electrons from the hydrogen atoms are more likely
to be found near the oxygen atom than the hydrogen
atoms
 Hydrogen Bonding – H2O 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
Bonding in Solids
•Bonds in solids can be of the
following types
OIonic OCovalent OMetallic
Ionic Bonds in Solids
•The dominant interaction between ions is
through the Coulomb force
•Many crystals are formed by ionic
bonding (I-VII, II-VI) e.g. NaCl
•Ions are closed electronic shells. [e.g.
LiF, Li (1s22s) becomes Li+ (1s2), F

(1s 2s 2p ) becomes F (1s22s22p6)]
2 2 5
Electrostatic Energy
•The net effect of all the interactions is a
negative electric potential energy
2
U  αk e
attractive
r
Oα is a dimensionless number known as the
Madelung constant
OThe value of α depends only on the
crystalline structure of the solid
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
 OThis 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
U to ta l  αk  m
r r
• The minimum value, U , is
o
called the ionic cohesive
energy of the solid
O It represents the energy
needed to separate the
solid into a collection of
isolated positive and
negative ions
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)
Na-Cl
Na + 5.14 eV → Na+ + e- (ionization
energy = 5.14 eV)


Cl + → Cl
e- + 3.61 eV
(electron affinity = 3.61 eV)

Na+ + Cl → NaCl + 7.9 eV
(cohesive energy = 7.9 eV)

i.e. the energy per molecule of NaCl is

(7.9 – 5.1 + 3.6) = 6.4 eV lower than
the energy of separated neutral
atoms.
More properties of Ionic Crystals
•They form relatively stable, hard
crystals
•They are poor electrical conductors
OThey contain no free electrons (filled shells)
OEach electron is bound tightly to one of the
ions
•They have high melting points
Properties of Solids with Covalent Bonds
•Properties include
OUsually very hard
•Due to the large atomic cohesive energies
OHigh bond energies
OHigh melting points
OGood electrical conductors
More about Covalent Bonds
 •Share electrons (usually 2 e-)
 •Directional (along orbital that share e-)
 •Electrons tend to localize between atoms
 •Prefer anti-parallel spins (Pauli)
 • A c t as “glue” toatoms
 • N o clear cut – range to be ionic orcovalent
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
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 (high
mobility)
 •The number of such mobile electrons in a metal is
large (high carrier density)
 •High electrical conductivity (& thermal)
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
 OVisible light is absorbed and re-emitted quite close
to the surface (reflective)
 OThis accounts for the shiny nature of metal surfaces
(screening, plasma frequency)
 •High electrical conductivity
 •More discussions on metal later….