Interatomic Binding

 All of the mechanisms which cause bonding between the atoms

derive from electrostatic interaction between nuclei and electrons.

 The differing strengths and differing types of bond are determined by

the particular electronic structures of the atoms involved.

 The existence of a stable bonding arrangement implies that the

spatial configuration of positive ion cores and outer electrons has less
total energy than any other configuration (including infinite separation
of the respective atoms).

 The energy deficience of the configuration compared with isolated

atoms is known as cohesive energy, and ranges in value from 0.1
eV/atom for solids which can muster only the weak van der Waals to
7ev/atom or more in some covalent and ionic compounds and some
metals.
 Energies of Interactions
Between Atoms
 The energy of the crystal is lower than that of the free
atoms by an amount equal to the energy required to
pull the crystal apart into a set of free atoms. This is
called the binding (cohesive) energy of the crystal.

 NaCl is more stable than a collection of free Na and Cl.

 Ge crystal is more stable than a collection of free Ge.

Cl Na NaCl
If neutral sodium and chlorine atoms found themselves closer
than 0.94 nm, it would be energetically favorable to transfer an
electron from Na to Cl and form the ionic bond.
  This typical curve has a
minimum at equilibrium
distance R0 V(R)
 R > R0 ;
 the potential increases
gradually, approaching Repulsive
0 as R∞
 the force is attractive
0 R0
 R < R 0; R
 the potential increases Attractive
very rapidly,
approaching ∞ at small R
r
separation.
 the force is repulsive

Force between the atoms is the negative of the slope of this curve.
At equlibrium, repulsive force becomes equals to the attractive part.
The potential energy of either atom will be given by:

V= decrease in potential energy+increase in potential energy

(due to attraction) (due to repulsion)

or simply:
a b
V (r )  m  n
r r
V(r): the net potential energy of interaction as function of r

r: the distance between atoms, ions, or molecules

a,b: proportionality constant of attraction and repulsion,

respectively

m, n: constant characteristics of each type of bond and type

of structure
 Types of Bonding Mechanisms
It is conventional to classify the bonds between
atoms into different types as

 Ionic,
 Covalent,
 Metallic,
 Van der Waals,
 Hydrogen.
 1 - IONIC BONDING

 Ionic bonding is the electrostatic force of attraction

between positively and negatively charged ions
(between non-metals and metals).
 These ions have been produced as a result of a transfer
of electrons between two atoms with a large difference
in electro negativities.
 All ionic compounds are crystalline solids at room
temperature.

 NaCl is a typical example of ionic bonding.

 The metallic elements have only up to the valence
electrons in their outer shell will lose their electrons
and become positive ions, whereas electronegative
elements tend to acquire additional electrons to
complete their octed and become negative ions, or
anions.

Na Cl
 NaCl
 Notice that when sodium loses its one valence electron it gets
smaller in size, while chlorine grows larger when it gains an
additional valance electron. After the reaction takes place, the
charged Na+ and Cl- ions are held together by electrostatic
forces, thus forming an ionic bond.
 When the Na+ and Cl- ions approach each other
closely enough so that the orbits of the electron in the
ions begin the overlap each other, then the electron
begins to repel each other by virtue of the repulsive
electrostatic coulomb force. Of course the closer
together the ions are, the grater the repulsive force.

 Pauli exclusion principle has an important role in

repulsive force. To prevent a violation of the exclusion
principle, the potential energy of the system increases
very rapidly.
 Property Explanation
The melting and boiling points of ionic compounds
Melting point are high because a large amount of thermal
and boiling point energy is required to separate the ions which are
bound by strong electrical forces.
Solid ionic compounds do not conduct electricity
when a potential is applied because there are no
Electrical
mobile charged particles.
conductivity
No free electrons causes the ions to be firmly
bound and cannot carry charge by moving.
Most ionic compounds are hard; the surfaces of
their crystals are not easily scratches. This is
Hardness
because the ions are bound strongly to the lattice
and aren't easily displaced.
Most ionic compounds are brittle; a crystal will
shatter if we try to distort it. This happens because
Brittleness
distortion cause ions of like charges to come close
together then sharply repel.
 2 - COVALENT BONDING
 Covalent bonding takes place between atoms with small
differences in electronegativity which are close to each
other in periodic table (between non-metals and non-
metals).
 The covalent bonding is formed by sharing of outer shell
electrons (i.e., s and p electrons) between atoms rather
than by electron transfer.
 This bonding can be attained if the two atoms each
share one of the other’s electrons.
 So the noble gas electron configuration can be attained.
 Each electron in a shared pair is attracted to both nuclei
involved in the bond. The approach, electron overlap, and
attraction can be visualized as shown in the following
figure representing the nuclei and electrons in a hydrogen
molecule.

e
Comparison of Ionic and
Covalent Bonding
 3 - METALLIC BONDING

 Metallic bonding is the type of

bonding found in metal
elements. This is the
electrostatic force of attraction
between positively charged ions
and delocalized outer electrons.

 The metallic bond is weaker

than the ionic and the covalent
bonds.
METALLIC BONDING
 Metallic structures are typically rather empty
(having large internuclear spacings) and prefer
lattice arrangements in which each atom has
many nearest neighbors.

 The weakness of the individual bonding actions in

a metal is due to the enlargement of the
internuclear spacing.
 Valance electrons are relatively bound to the nucleus and
therefore they move freely through the metal and they are
spread out among the atoms in the form of a low-density
electron cloud.

A metallic bond result from the

sharing of a variable number of + + +
electrons by a variable number of

atoms. A metal may be described
+ + +
as a cloud of free electrons.

 Therefore, metals have high + + +

electrical and thermal conductivity.
 All valence electrons in a metal combine to form a “sea” of
electrons that move freely between the atom cores. The
more electrons, the stronger the attraction. This means the
melting and boiling points are higher, and the metal is
stronger and harder.
 The positively charged cores are held together by these
negatively charged electrons.
 The free electrons act as the bond (or as a “glue”) between
the positively charged ions.
 This type of bonding is nondirectional and is rather
insensitive to structure.
 As a result we have a high ductility of metals - the “bonds”
do not “break” when atoms are rearranged – metals can
experience a significant degree of plastic deformation.
 The Uncertainty Principle has two important implications:

a. We cannot measure the position of a particle without

disturbing it. In classical physics it is assumed that we are
passive observers of the universe.
In quantum physics observing the universe necessarily disturbs it
and so to describe what is occurring, physics needs to include the
observer in the description.
b. In classical physics we can measure everything precisely.
There may be practical problems but there is no principle
preventing precise measurements.
In quantum physics we cannot measure position and momentum
both precisely and so there can be no determinism.
 Zero-Point Energy

If a particle is confined to a region 0 < x < a then in classical physics

it can also be at rest and so have no kinetic energy. In quantum
physics this is not the case. There must be uncertainty in the
momentum because of the Uncertainty Principle and so the particle
must on average be in motion and have some kinetic energy. The
uncertainty in the momentum and hence the minimum momentum
is p ~ ħ/a.
The minimum kinetic energy is ( ½)mv2 = p2/2m ~ħ2/(2ma2)
This minimum energy is called the zero point energy and exists
whenever a particle is confined.
The result that a particle can have zero-point energy
E ~ħ2/(2ma2) can be used to estimate a number of properties
and to make some important physical deductions easily.
In the case of nuclei of size 1 fm. The zero point energy is
10 MeV for protons or neutrons and 10000 MeV for electrons.
The former is typical for nuclear reaction energies and binding
energies while the latter is much larger. We conclude that there
are protons and neutrons in the nucleus but that there are not
free electrons.
 The ground state energy for the quantum harmonic
oscillator can be shown to be the minimum energy allowed
by the uncertainty principle.
The energy of the quantum harmonic oscillator must be at
least
E = (K.E) + P.E

Taking the lower limit from the uncertainty principle

Then the energy expressed in terms of the position

uncertainty can be written
 Minimizing this energy by taking the derivative with respect
to the position uncertainty and setting it equal to zero gives

Solving for the position uncertainty gives

Substituting gives the minimum value of energy allowed.

This is a very significant physical result because it tells us
that the energy of a system described by a harmonic
oscillator potential cannot have zero value. Physical
systems such as atoms in a solid lattice or in polyatomic
molecules in a gas cannot have zero energy even at
absolute zero temperature. The energy of the ground
vibrational state is often referred to as "zero point
vibration". The zero point energy is sufficient to prevent
liquid helium-4 from freezing at atmospheric pressure, no
matter how low the temperature is.
 4 - VAN DER WAALS BONDING
 It is a weak bond, with a typical strength of 0.2 eV/atom.
 It occurs between neutral atoms and molecules.
 The explanation of these weak forces of attraction is that
there are natural fluctuation in the electron density of all
molecules and these cause small temporary dipoles
within the molecules. It is these temporary dipoles that
attract one molecule to another. They are called van der
Waals' forces.

 The bigger a molecule is, the easier it is to polarise (to

form a dipole), and so the van der Waal's forces get
stronger, so bigger molecules exist as liquids or solids
rather than gases.
 The shape of a molecule influences its ability to form
temporary dipoles. Long thin molecules can pack closer to
each other than molecules that are more spherical. The
bigger the 'surface area' of a molecule, the greater the van
der Waal's forces will be and the higher the melting and
boiling points of the compound will be.
 Van der Waal's forces are of the order of 1% of the strength
of a covalent bond.

Homonuclear molecules,
such as iodine, develop
temporary dipoles due to
natural fluctuations of electron
density within the molecule
Heteronuclear molecules,
such as H-Cl have permanent
dipoles that attract the opposite
pole in other molecules.
The dipoles can be formed as a result of unbalanced distribution
of electrons in asymettrical molecules. This is caused by the
instantaneous location of a few more electrons on one side of the
nucleus than on the other.

symmetric asymmetric
Therefore atoms or molecules containing dipoles are attracted
to each other by electrostatic forces.

Display a marked
No attraction is produced
attractive forces
 These forces are due to the electrostatic attraction
between the nucleus of one atom and the electrons of
the other.

 Van der waals interaction occurs generally between

atoms which have noble gas configuration.

van der waals

bonding
 5 – HYDROGEN BONDING
 A hydrogen atom, having one electron, can be covalently
bonded to only one atom. However, the hydrogen atom
can involve itself in an additional electrostatic bond with a
second atom of highly electronegative character such as
fluorine or oxygen. This second bond permits a hydrogen
bond between two atoms or strucures.
 The strength of hydrogen bonding varies from 0.1 to 0.5
ev/atom.
 Hydrogen bonds connect water
molecules in ordinary ice.
Hydrogen bonding is also very
important in proteins and
nucleic acids and therefore in
life processes.
 Zero Point Energy

In a quantum mechanical system such as the particle in a

box or the quantum harmonic oscillator, the lowest possible
energy is called zero-point energy.
Zero-point energy is the lowest possible energy that a
quantum mechanical physical system may have; it is the
energy of its ground state. All quantum mechanical systems
undergo fluctuations even in their ground state and have an
associated zero-point energy, a consequence of their wave-
like nature. The uncertainty principle requires every physical
system to have a zero-point energy greater than the
minimum of its classical potential well, even at absolute zero.
For example, liquid helium does not freeze under
atmospheric pressure at any temperature because of its
zero-point energy.
Zero-point energy is the energy that remains when all other energy
is removed from a system. This behaviour is demonstrated by, for
example, liquid helium. As the temperature is lowered to absolute
zero, helium remains a liquid, rather than freezing to a solid, owing to
the irremovable zero-point energy of its atomic motions. (Increasing
the pressure to 25 atmospheres will cause helium to freeze.)
A harmonic oscillator is a useful conceptual tool in physics. Classically
a harmonic oscillator, such as a mass on a spring, can always be
brought to rest. However a quantum harmonic oscillator does not
permit this. A residual motion will always remain due to the
requirements of the Heisenberg uncertainty principle, resulting in a
zero-point energy, equal to 1/2 hf, where f is the oscillation frequency.
The concept of zero-point energy was developed in Germany by
Albert Einstein and Otto Stern in 1913, using a formula developed by
Max Planck in 1900.
Vacuum energy is the zero-point energy of all the fields in space,
which in the Standard Model includes the electromagnetic field, other
gauge fields, fermionic fields, and the Higgs field. It is the energy of
the vacuum, which in quantum field theory is defined not as empty
space but as the ground state of the fields. In cosmology, the vacuum
energy is one possible explanation for the cosmological constant. A
related term is zero-point field, which is the lowest energy state of a
particular field.
In conventional quantum physics, the origin of zero-point energy is
the Heisenberg uncertainty principle, which states that, for a
moving particle such as an electron, the more precisely one
measures the position, the less exact the best possible
measurement of its momentum (mass times velocity), and vice
versa. The least possible uncertainty of position times momentum
is specified by Planck's constant, h. A parallel uncertainty exists
between measurements involving time and energy (and other so-
called conjugate variables in quantum mechanics). This minimum
uncertainty is not due to any correctable flaws in measurement,
but rather reflects an intrinsic quantum fuzziness in the very nature
of energy and matter springing from the wave nature of the
various quantum fields. This leads to the concept of zero-point
energy