Atomic Bonding

Many solids are aggregates of atoms. The bonds are made of attractive and repulsive forces that tend to
hold the adjacent atoms or atomic units at a particular spacing such that the opposite forces just
balance; and the process of holding them together is known as bonding. Particular type of bonding
within a material plays a major role in determing the physical, chemical and electrical properties of
material. Different charge distribution give rise to different types of bonding. They are conveniently
divided into five classes. They are: (i) ionic bonding, (ii) covalent bonding, (iii) metallic bonding, (iv)
hydrogen bonding, (v) van der Waals bonding. Based on the bond strength, atomic bondings can be
grouped into primary and secondary bondings. Primary bondings have bond energies in the range of 0.1-
10 eV/bond. Ionic, covalent and metallic bondings are generally stronger than the metallic bonding.
However among these, ionic and covalent bondings are generally stronger than the metallic bondings.
On the other hand, secondary bonding have energies in the range 0.01 – 0.5 eV/bond, one or two orders
of magnitude smaller than those of primary bondings. Hydrogen bonding and vander Waals bondings
are examples of secondary bondings. Generally, van der Waals bonding is the weakest of all.

Ionic Bonding and Ionic crystal:

An ionic bonding can only be formed between two different atoms, one electropositive and other
electronegative. Electropostive elements readily give up electrons and are usually Group I or II elements,
eg. Na, K and Ba whereas electronegative elements readily take up electrons and are typically Group VI
or VII elements eg. Cl, Br and O. As an example of ionic bonding, consider a molecule of common salt,
NaCl. When neutral atoms of Na an Cl are brought close together it is easy for the outer valence electron
of the sodium atom to be transferred to the chlorine atom so that both of them acquire a stable inert
gas electronic configuration as shown in fig1.
Such configuration will have nearly spherically symmetric charge distribution around the ions with some
distortion near the region of contact between neighbouring atoms. Since the sodium cation carries a
positive charge and the chlorine anion a negative charge there exists an electrostatic attraction between
the two ions. Actually, a negative charge attracts all positive charges in the neighbourhood, and vice
versa. Consequently,in the crystalline solid Na+ ions will be surrounded by Cl- ions and Cl- ions by Na+
ions in such a way that the attraction between the neighbouring unlike charges exceeds the repulsion
due to like charges. The resulting sodium chloride structure is shown in fig2.

An ionic crystal is a crystal consisting of ions bound together by their electrostatic attraction. Examples
of such crystals are the alkali halides, including potassium fluoride, potassium chloride, potassium
bromide, potassium iodide, sodium fluoride, and other combinations of sodium, caesium, rubidium, or
lithium ions with fluoride, bromide, chloride or iodide ions.

Covalent Bonding and covalent network crystal:

Elements from the central groups of the periodic table, notably group IV are not readily reduced to a
closed shell electronic configuration because the energy required to remove all the valence electrons is
too large, and so ionic bonding is unlikely. Also, when atoms in a crystal have similar electronegatives,
bond formation occurs through the sharing of valence electrons (not through transfer of electrons as in
ionic case), each atom contributing one electron or more to the bond. This sharing of electrons gives rise
to covalent bonding. The simplest case of covalent bonding occurs in the hydrogen molecule in which
two hydrogen atoms contribute their 1S1 electrons to form an electron-pair covalent bond. When the
two atoms come together to form hydrogen molecule, their electron clouds interact and overlap. The
probability of finding the 1S1 electrons of the atoms is maximum between the two nuclei in the
hydrogen molecule as shown in fig 3. Since Pauli’s exclusion principle cannot be violated, the shared
electrons therefore must have opposite spins. The force of attraction between the atoms arises from the
interaction of these antispin electrons. The electrostatic repulsion between the electrons keeps the
atoms at an equilibrium distance where the two forces are equal, or the potential energy is minimum. A
hydrogen molecule formed under this situation will have stable configuration.
The directional nature of the covalent bond results from the restricted orbital motion of the electrons.
The shapes of atomic orbitals s (l =0) and p (l = 1) are shown in fig 4. In p-orbitals, the shapes represent
the angular dependence (directional) distribution of electron density.

For example we consider the case of water molecule. In the bond formation, the two hydrogen atoms
use 1s orbitals. The electronic configuration of oxygen is 1s2 2s2 2px1 2py1 2pz2, which shows that px and
py orbitals should be used. Fig 5 shows the xy plane of water molecule. It is observed that px and py
orbitals lie mutually perpendicular to each other in xy plane. To obtain a maximum possible overlap
between 1s orbitals of hydrogen atoms and px and py orbitals of oxygen atom, it is necessary for
hydrogen atoms to approach along the x an y axes. This leads to the overlap shown in Figure 5, and the
HOH bond angle should amount to 90 dgree. It is experimentally observed that the value of actual angle
is 104.5 degree which is due to the repulsion between the two hydrogen atoms.
A covalent network crystal consists of atoms at the lattice points of the crystal, with each atom being
covalently bonded to its nearest neighbor atoms (see figure below). The covalently bonded network is
three-dimensional and contains a very large number of atoms. Network solids include diamond, quartz,
many metalloids, and oxides of transition metals and metalloids. Network solids are hard and brittle,
with extremely high melting and boiling points. Being composed of atoms rather than ions, they do not
conduct electricity in any state.

Metallic bonding and Metallic Crystal:

Metallic bonding, the final primary bonding type, is found in metals and their alloys. A relatively simple
model has been proposed that very nearly approximates the bonding scheme. Metallic materials have
one, two, or at most, three valence electrons. With this model, these valence electrons are not bound to
any particular atom in the solid and are more or less free to drift throughout the entire metal. They may
be thought of as belonging to the metal as a whole, or forming a ―sea of electrons‖ or an ―electron
cloud.‖ The remaining nonvalence electrons and atomic nuclei form what are called ion cores, which
possess a net positive charge equal in magnitude to the total valence electron charge per atom. Figure 6
is a schematic illustration of metallic bonding.
The free electrons shield the positively charged ion cores from mutually repulsive electrostatic forces,
which they would otherwise exert upon one another; consequently the metallic bond is nondirectional
in character. In addition, these free electrons act as a ―glue‖ to hold the ion cores together Bonding
may be weak or strong; energies range from 0.7 eV/atom for mercury to 8.8 eV/atom for tungsten. Their
respective melting temperatures are -39 and 3410 oC. Metallic bonding is found for all elemental
metals. Metallic crystals are held together by metallic bonds, electrostatic interactions between cations
and delocalized electrons. These crystals sparkle with the lustrous sheen we think of metals having. They
are extremely good conductors of heat and electricity.

Van Der Waals Bonding and Inert gas crystals:

Secondary, van der Waals, or physical bonds are weak in comparison to the primary or chemical ones;
bonding energies are typically on the order of only 10 kJ/mol (0.1 eV/atom). Secondary bonding exists
between virtually all atoms or molecules, but its presence may be obscured if any of the three primary
bonding types is present. Secondary bonding is evidenced for the inert gases, which have stable electron
structures, and, in addition, between molecules in molecular structures that are covalently bonded.

Secondary bonding forces arise from atomic or molecular dipoles. In essence, an electric dipole exists
whenever there is some separation of positive and negative portions of an atom or molecule. The
bonding results from the coulombic attraction between the positive end of one dipole and the negative
region of an adjacent one, as indicated in Figure 7.

Dipole interactions occur between induced dipoles, between induced dipoles and polar molecules
(which have permanent dipoles), and between polar molecules. Hydrogen bonding, a special type of
secondary bonding, is found to exist between some molecules that have hydrogen as one of the
constituents.

Fluctuating Induced Dipole Bonds:

A dipole may be created or induced in an atom or molecule that is normally electrically symmetric; that
is, the overall spatial distribution of the electrons is symmetric with respect to the positively charged
nucleus, as shown in Figure 8a.
All atoms are experiencing constant vibrational motion that can cause instantaneous and short-lived
distortions of this electrical symmetry for some of the atoms or molecules, and the creation of small
electric dipoles, as represented in Figure 8b. One of these dipoles can in turn produce a displacement of
the electron distribution of an adjacent molecule or atom, which induces the second one also to become
a dipole that is then weakly attracted or bonded to the first; this is one type of van der Waals bonding.
These attractive forces may exist between large numbers of atoms or molecules, which forces are
temporary and fluctuate with time.

Polar Molecule-Induced Dipole Bonds:

Permanent dipole moments exist in some molecules by virtue of an asymmetrical arrangement of

positively and negatively charged regions; such molecules are termed polar molecules. Figure 9 is a
schematic representation of a hydrogen chloride molecule; a permanent dipole moment arises from net
positive and negative charges that are respectively associated with the hydrogen and chlorine ends of
the HCl molecule. Polar molecules can also induce dipoles in adjacent nonpolar molecules, and a bond
will form as a result of attractive forces between the two molecules. Furthermore, the magnitude of this
bond will be greater than for fluctuating induced dipoles.

Permanent Dipole Bonds:

Van der Waals forces will also exist between adjacent polar molecules. The associated bonding energies
are significantly greater than for bonds involving induced dipoles. The strongest secondary bonding
type, the hydrogen bond, is a special case of polar molecule bonding. It occurs between molecules in
which hydrogen is covalently bonded to fluorine (as in HF), oxygen (as in H2O), and nitrogen (as in NH3).
For each H—F, H—O, or H—N bond, the single hydrogen electron is shared with the other atom. Thus,
the hydrogen end of the bond is essentially a positively charged bare proton that is unscreened by any
electrons. This highly positively charged end of the molecule is capable of a strong attractive force with
the negative end of an adjacent molecule, as demonstrated in Figure 10 for HF. In essence, this single
proton forms a bridge between two negatively charged atoms.The magnitude of the hydrogen bond is
generally greater than that of the other types of secondary bonds and may be as high as 0.52
eV/molecule.
Molecular crystals typically consist of molecules at the lattice points of the crystal, held together by
relatively weak intermolecular forces. The intermolecular forces may be dispersion forces in the case of
nonpolar crystals, or dipole-dipole forces in the case of polar crystals. Some molecular crystals, such as
ice, have molecules held together by hydrogen bonds. When one of the noble gases is cooled and
solidified, the lattice points are individual atoms rather than molecules. In all cases, the intermolecular
forces holding the particles together are far weaker than either ionic or covalent bonds. As a result, the
melting and boiling points of molecular crystals are much lower. Lacking ions or free electrons,
molecular crystals are poor electrical conductors.

Forces between atoms

Matter can exist in solid state only because there are forces of interaction acting between the atoms
when they are brought close to each other. For a solid to have stable structure, the forces of interaction
between the atoms should be of two types: attractive, to prevent the atoms from moving away from
each other, and repulsive, to prevent the atoms from merging. Let us consider the general situation of
two identical atoms in their ground states with an infinite separation (having interaction potential
energy equal to zero). Let the atoms consist of moving electrical charges and will either attract or repel
each other when they are brought close together. As the atoms approach, the attractive forces increase
and the potential energy increase in a negative sense (the energy of attraction is negative since the
atoms do work of attraction). When they are at a separation of a few atomic diameters, repulsive forces
begin to asserts themselves (the repulsive energy is positive because external work must be done to
bring two such atoms close together). This is short range in nature which prevents the crystal from
collapsing indefinitely. Actually the attractive forces between the atoms bring them close together until
the individual electron clouds begin to overlap and a strong repulsive force arises to comply with Pauli’s
exclusion principle. At a certain separation, called the equilibrium separation Re at which the attractive
and repulsive forces are equal, the two atoms are in stable situation and have minimum potential
energy.
 Lattice Energy of Ionic Crystal
The cohesive energy of a crystal is defined as the energy that must be added to the crystal to
separate its components into neutral free atoms at rest, at infinite separation, with the same
electronic configuration. The term lattice energy is defined as the energy that must be added to
the crystal to separate its component ions into free ions at rest at infinite separation.

The bond energy of a molecule held together by an ionic bond is not the same as the cohesive
energy of the crystal, because in the crystal each ion interacts with all the other ions present
and not just with one, two or three of the opposite sign.

Let us now consider the case of NaCl which is one of the best examples of an ionic compound.
The stability of an ionic crystal depends on the balancing of atleast three forces: the
electrostatic or Coulomb forces between the ions which give a resultant attraction falling off
with the square of the distance; vander Waals forces of attraction diminishing according to the
seventh power of the distance (usually neglected); and the interionic repulsive forces falling off
still more rapidly with distance. The resultant of the attractive and repulsive forces is to lead to
an equilibrium position of minimum potential energy; i.e. of greatest stability as shown in Fig 1.