Atomic bonding in solids

(based on ch. 37 Tipler and ch 2 Callister)

the physical properties of materials

From the interatomic forces that bind the

atoms together.
Start: Two atoms at certain distance

Analyze the forces

Influence of other atoms in the solid

r
Type of forces

FA attractive
FR repulsive
FA and FR are functions of
interatomic distance
FR quantum mechanical by
nature (result of exclusion
principle, electrons dont
sit on top of each other)

Remember the gradient of the

potential energy is the force
 Atoms far apart wave functions for core electrons do not
overlap

Electrons can be distinguished by the atom (ion) that they belong to

(can have same quantum numbers)

Atoms close together wave functions for core electrons

overlap
Electrons must go to higher orbits energy is REQUIRED to shift
them

Increase in energy EQUIVALENT to REPULSION

 Forces and Bond Length
At large distance: attractive electrostatic
forces
At short distance: repulsive quantum
mechanical force
Where force is zero atoms are in
equilibrium, this separation is the bond
length.
Total force is FN = FA + FR
At distance r0 these forces cancel FA + FR = 0 and the
atoms are in their EQUILIBRIUM POSTION r0
 Potential Energy Picture for Bonding
E0 bonding energy

Large E0 - solids Potential

energy

Intermediate E0 - liquids ER

Low E0 - gases

EN r
E0

Potential energy E = Fd r z r0
EA
 Primary Bonds

Strength of bonding types varies

Many properties of materials depend on the
type of bonding (melting point, stiffness,
electric and thermal conductivity, many
others)
Three main types of bonding
Ionic
Covalent
Metallic
Will discuss van der Waals bonds later in
course
 Ionic Bonding

Found in salts (Na+Cl-)

Valence electrons exchanged between atoms
so that all individual atoms acquire stable
electron configuration
Ionization energy for 3s1 electron - 5. 14 eV
3s1 removed positive ion with spherically
symmetric closed shell electron core
Cl 3p5 ground state configuration
Def: Electron affinity energy released by an
atoms acquisition of an electron
 For Cl electron affinity = 3.62 eV
Net energy needed to form Na+ and Cl-
ions I.E. E.A. = 1. 52 eV
These ions then attract
each other to form bond
E
(eV)

1.52 eV
r
4.27eV

r0=2.36 Ions are charged and attract

each other reducing potential energy
 A
EA
r Ionic bond is non-directional
- Magnitude of the bond is equal in all
B directions around an ion
ER n
r
For ionic bond bonding energies are relatively large

Relatively high melting point

Brittle, electrically and thermally

insulating
 Covalent bonding

Stable configuration by sharing

of electron between adjacent
atoms.
Covalent bonding
Directional
Quantum mechanical
interference effect
Symmetry properties of the wave function of electrons

close
Far apart
Buckyballs (of fullerenes): Covalent bonds are
directional so resulting molecules have
strange shapes

C60 C540
 Covalent bonding

in many non-metallic elements

H2, Cl2, F2,
In elemental solids
C, Si, Ge
Covalent bonds
typically (but not always!) a strong bond, can
be very strong (diamond)
polymer materials typify this bond
 Two dissimilar atoms bonding
Often a mixture of covalent and ionic bonding

A measure of degree to which the bond is ionic or

covalent is the electric dipole moment

Often a percentage of ionic or covalent bonding is

quoted (can be guessed from electronegativities)
(Electric dipoles will be discussed more later in the course)
Electric Dipole moment is the charge that moves to form the bond multiplied by the
distance it has moved: can be measured in experiments, as can the bond length

-q r0 +q

A 100% ionic bond for ions of charge one like NaCl

would have dipole moment er0
 Metallic bonding

Metallic materials
with 1, 2, 3 valence electrons
Model
valence electrons NOT bound to any particular
atom in the solid
Electrons are free to drift through the metal
electron sea
Atomic nuclei and nonvalence electrons make ion
core
Ion core has net positive charge=total valence
electron charge/atom
 Metallic bond

Non-directional
Free electrons act like glue
Can be weak or strong

Melting points vary a lot

Group IA and II B
Good conductors (heat and electricity)
 Consequences of different types of
bonding
Melting point function of the interatomic distance
(bonding energy)
The higher the bonding energy the higher melting temperature

Stiffness modulus of elasticity depends on the shape of

the curve of force versus atomic separation.
Electrical conductivity depends on interatomic bonds
Metalic good conductors
Ionic, covalent insulators or semiconductors

The magnitude of the coefficient of thermal expansion

is dependent upon potential energy versus interatomc
distance.
Elasticity (next week) Linear dependence
of force

Modulus of elasticity: about

the equilibrium point the
force is a roughly linear
function of distance.

This suggests Hookes law

behaviour as a solid is
compressed.

How does the strength of the

bond affect the stiffness?