COVALENT CRYSTALS

In atoms with filled outer most shells, the electron overlap can only be accommodated with the
excitation of electrons to higher energy levels. In covalent compounds, this overlap can be
accommodated without the excitation of electrons to higher energy states. This reduces the
repulsive interaction and the compound have shorter bond lengths.
Covalent, valance or homo-polar bond is an electron pair bond in which two atoms share two
electrons. As a result of the sharing, the electron charge density is higher in the region between
the two atoms. The number of covalent bonds each atom can make is limited by the number of
missing electrons in the outer most (completely filled) shell of that atom. For example, a
carbon atom can join with four other carbon atoms at a tetrahedral angle (109.5) in diamond
structure. Similar structures occur in Germanium and Silicon.
Basic difference between the ionic and covalent crystal is the distribution of charge in the
region between the atoms. In the ionic crystals, the electron charge density along the first line
varies much. For example, in NaCl, it reduces to 0.1 electron per cubic angstrom (1/Å). On the
other hand, in covalent crystals, the variations in the charge is not small. For example in
diamond, it does not reduce below five electrons per cubic angstrom (1/Å)as shown in the
figure.

The covalent bonds are formed in

i. most organic compounds
ii. between the pairs of halogen atoms (Cl, F, Br) in solid and fluid form. Also the bonds
of hydrogen, nitrogen and oxygen are covalent.
iii. elements of Group-IV.
iv. group V such as chains of arsenic in IV such as diamond, silicon and germanium.
v. compounds obeying 8N rule such as InSb. This is subject to the condition that the
horizontal separation between elements is not too large.

It is often noted that the compounds with covalentbonds can exist in allotropic forms i.e. they have
polymorphs. Itmeans that one form can be changed into another by the change oftemperature and/or
pressure.Once the change occurs, the materialcan retain itself for a long time in the changed state.
Forexample,ZnS (zinc blend) is cubic and can be transformed intohexagonalstructure (wurtzite). Diamond
and graphite is anothercommon example. Covalent compounds, like diamond has a looselypacked
structureand the carbon atoms in diamond occupy only 34%of the available space as compared to 74% in
hexagonal closepacked structures.
In diamond each atom has four neighbours and each bondinvolves a pair of neighbours. Hence there are
two bonds peratom. Each atom has four electrons in its outer most shell. Sincethere are four available
electrons per atom and two bonds peratom, so there are two electrons per bond, which is a rightnumber
for saturation.

In diamond
4-nearest neighbours
1-bond involves two neighbours
2-bonds per atom
4-electrons are contributed by each atom, so
2-electrons per bond are there in diamond.
In Na
8-nearest neighbours
1-bond involves two neighbours
4-bonds per atom
1-electron is contributed per atom, so
l/4- electron is available for each bond.
Since each bond involves two electrons, so there is a deficiencyof electrons per bond.

The METALS:
Metallic structures are empty and prefer latticearrangements in which each atom has many nearest
neighbours.Metals are typically crystallized in FCC, BCC or HCP structuresand each atom has 12, 8 and
12 nearest neighbours respectively.The simplest metal is a monovalent alkali metal. Here each
atomcontribute one valence electron to the common pool of electrons.For example Li, which has only one
electron outside the completeK-shell. The individual bonds are weak in metals and this isdemonstrated by
an enlargement in inter-nuclear spacing comparedwith that in diatomic molecules. For example Li-Li
distance insolid lithium is 3.04Å, where as it is 2.67Å in covalently bondedLi molecule. However, the
total binding energy increases insolid metals as compared to separatemolecules. This is becausein solids,
there are many more bonds. The binding energy per atomincreases from 0.6eV with Li to 1.8eV in solid
lithium.
How a piece of metal is kept together? The simplest answer is:byelectrostatic forces. The metallic bond is
similar to theionicbond in the sense, the main role is played by the electrostaticforces.But there is
adifference as for as the position ofcharges is concerned.In metals the carriers of negativechargearehighly
mobile and the bonds formed have somewhatdifferentproperties. Since the electrons move around and
visit everylittle part of the metal, the electrostatic forces come from alldirections. The electrons in a metal
are regarded as a glue whichholds the metaltogether.This is the reason that a smalldeformation doesnot
causefracture in metals. Whether wecompress or try to pull apart a piece of metal, the cohesiveforces are
still there. That is why the metals are outstandinglyductile and malleable.