10/23/2020

ATOMIC BONDING
IN SOLIDS

BONDING ENERGY, INTERATOMIC SPACING

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The cohesive forces that hold a solid together

are directly related to the interatomic bonding
within the solid.
For two ions to come closer to each other, two
types of forces are in effect.
Attractive Forces (+) pull atoms together
Repulsive Forces (-) develop when atoms are
brought into close proximity (~nm).
There is mutual electronic repulsion between the
two atoms because of the electrons around an
atoms.

Relation between the magnitude of

the forces and the interatomic
distances

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 When two atoms approach each other they exert forces

on one another.
 As the ions come closer together, they will be attracted
by coulombic forces (nucleus of one ion will attract the
electron charge cloud of the other, and vice versa).
 When the ions come still closer together, eventually their
two electron charge clouds will interact and repulsive
forces will arise.
1. Forces of attraction (Fa)→Attractive forces b/w
atoms decrease with interatomic spacing, x.
(is inversely proportional with x)
2. Forces of repulsion (Fr)→As atoms come closer,
repulsive forces dominate.
(is inversely proportional to a higher power of x than Fa)

 Total force SF = Fa+Fr (summation of attractive and

repulsive forces)
 When Fa=Fr → Equilibrium point → @ x=x0
There will be no net force between the ions
and they will remain at an equilibrium
seperation distance, the interionic distance x0.
 x0 is also known as equilibrium spacing and is
a very specific distance for a given pair of
atoms or ions. When equilibrium is attained,
the distance between the two atoms is equal
to the sum of their radii. A large amount of
force is needed to change (stretch or
compress) that distance. Therefore, generally
atoms can be assumed as hard balls when
atomic arrangements are considered.

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x0
Tensile (+)

Fa(x): Attractive force

Ft(x): Total force
Force

x,Interatomic Spacing
Compressive (-)

Fr(x): Repulsive force

Bond Energy
• Sometimes it is more convenient to work with the potential
energies between two atoms instead of forces.
where En, Ea, Er are the net,
E   Fdx attractive and repulsive energies for
For atomic systems two isolated and adjacent atoms.
x
The net potential energy E between
En   Fdx
a pair of oppositely charged ions,

x0
for example Na+Cl-, which are
En   ( Fa  Fr )dx brought closer together is equal to

the sum of the energies associated
with the attraction and repulsion of
En  Ea  Er
the ions.

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@ x  x0
x0

Eb   Fdx


The net energy is a minumum when the

ions are at their equilibrium seperation
distance xo. At minimum energy, the force
between the ions is zero.

Eo or Eb is the bonding energy that

represents the energy required to separate
two atoms to an infinite separation.

The magnitude of the bonding energy and

the shape of E-x curve vary from material to
material and they both depend on the atomic
bonding.
Furthermore a number of material properties
depend on atomic relationships (Eb, curve
shape and bond type).
Melting point
Hardness
Modulus of Elasticity=dF/dx at x=x0
Thermal expansion
Conductivity of metals

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Energy and Packing

• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.

Relation Between Some Material Properties to

the Atomic Bonding Characteristics

Since all materials are made of atoms, obviously the properties of

all materials are related to their atomic structure.
1. Density: is controlled by atomic weight, atomic radius, and
coordination number (number of adjacent atoms surrounding
a reference atom). Coordination number is an important
factor since it controls the atomic packing.
2. Melting and Boiling Temperature: can be correlated with the
depth of the energy-interatomic spacing curve. A greater
depth of curve means that a higher energy is required to
seperate the atoms leading to a higher melting temperature
for the material.

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Relation Between Some Material Properties to

the Atomic Bonding Characteristics

3. Strength: deeper energy curve occurs when the interatomic

forces of attraction are higher. Since the deeper energy curve
also leads to higher melting points, materials with higher
melting points are often the stronger (harder).
4. Modulus of Elasticity: can be calculated from the slope of the
net force curve. For deeper energy curves (for stronger
material), the slope of this net force curve increases.
5. Thermal Expansion: is related to atomic packing factor and
vary inversely with the melting temperatures.
6. Electrical and Thermal Conductivity: Electrical conductivity is
dependent on the type of atomic bond.

Relation Between Some Material Properties to

the Atomic Bonding Characteristics

7. Optical Properties: metalically bonded materials become

opaque to transmitted light since the freely moving electrons
can absorb the light energy.
8. Chemical Properties: in general chemical properties are
related to the valance electrons and formation or disruption
of bonds.

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Factors Affecting the Atomic Radius or

Equilibrium Distance
1. Temperature: An increase in temperature increases
the energy. Any increase in energy above the
minimum point will increase the equilibrium distance
(x0) because of asymmetric shape of the energy
curve.

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Factors Affecting the Atomic Radius or

Equilibrium Distance
2. Ionic Value: A negative ion is larger than its corresponding
atom. Since there are more electrons surrounding the nucleus
than there are protons in the nucleus, the electrons added to the
atom are not as closely attracted to the nucleus as were the
original ones. An electropositive atom (Fe+2) has a smaller radius
than a neutral atom (Fe).

Similarly an
electronegative
atom (O-2) has a
higher radius
than a neutral
atom (O).

3. Surrounding (Adjacent) Atoms: As the number

of surrounding atoms around a bond
increases, the interatomic distance increases
due to the repulsive forces developed by
electrons.
4. Covalency: As the number of shared electrons
increases, atoms will attract each other more
(stronger bond) and the radius decreases.

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Example : r: Interatomic distance in nm (*10-9 m)

A B A: -7.2 * 10-20 [J (nm)2]
U= + [J]
rm rn
B: 9.4 * 10-25 [J (nm)10]
U is energy
m = 2, n = 10
-7.2 * 10-20 9.4 * 10-25
U= +
r2 r10
Find r0 where the bond is most stable? Energy is minimum
Calculate the net energy?

dU U = A r-m + B r-n
=0
dr dU
= -m A r-m-1 – n B r-n-1
dr

dU
= -2 * (-7.2*10-20) * r-3 – 10*(9.4*10-25)*r-11 = 0
dr

14.4*10-20 9.4*10-25
= → r8 = 6.53*10-5
r3 r11
r = 0.299 nm

-7.2*10-20 + 9.4*10-25
Umin = = -6.40*10-19 [J]
(0.299)2 (0.299)10

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