PHY 3201 FIZIK KEADAAN PEPEJAL

From Last Class

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.
Interatomic Binding
PHY 3201 FIZIK KEADAAN PEPEJAL
The potential energy of either atom will be given by:



or simply:
V= decrease in potential energy+increase in potential energy
(due to attraction) (due to repulsion)
( )
m n
a b
V r
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
PHY 3201 FIZIK KEADAAN PEPEJAL
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.
PHY 3201 FIZIK KEADAAN PEPEJAL
Van der waals interaction occurs generally between atoms which
have noble gas configuration.

van der waals
bonding
PHY 3201 FIZIK KEADAAN PEPEJAL
Ionic Bonding
In an ionic crystal, an electron is essentially
transferred from one type of atom to another.
The ionic bond results from the electrostatic
interaction of oppositely charged ions.

e.g. Na + Cl Na
+
+ Cl
-

PHY 3201 FIZIK KEADAAN PEPEJAL
Ionic bonding in NaCl

3s
1
3p
7
Sodium
Atom
Na
Chlorine
Atom
Cl
Sodium Ion
Na
+
Chlorine Ion
Cl
-
PHY 3201 FIZIK KEADAAN PEPEJAL
Example
The transfer of an electron from Na atom to Cl atom to form a
Na
+
-Cl
-
ion pair =ionization energy of Na electron affinity of Cl=
5.1-3.6 = 1.5 eV
The cohesive energy of NaCl molecule due to the interaction
potential = -7.9
Total cohesive energy per NaCl molecule = -7.9 + 1.5 =-6.4 eV
PHY 3201 FIZIK KEADAAN PEPEJAL
An ion i at a particular lattice site is considered and its
interaction with all its neighbouring ions are added.
The energy is written as;



The Coulomb term for both like and unlike charges

=
j
ij i
U U
|
|
.
|

\
|
=
ij
Coulomb
r
q
U
2
PHY 3201 FIZIK KEADAAN PEPEJAL
The repulsive term due to overlap of electrons clouds


Therefore



Since the repulsive term is effective only at very short
distances, U
ij
can be split into two parts
|
|
.
|

\
|

=

ij
repulsive
r
U exp
|
|
.
|

\
|

|
|
.
|

\
|

=
ij
ij
ij
r
q
r
U
2
exp

PHY 3201 FIZIK KEADAAN PEPEJAL

For nearest neighbours, where R is the nearest
neighbour


and for other ions

expressing r
ij
as p
ij
R

|
|
.
|

\
|

|
|
.
|

\
|
=
R
q R
U
ij
2
exp

|
|
.
|

\
|
=
ij
ij
r
q
U
2
|
|
.
|

\
|
=
R p
q
U
ij
ij
2
PHY 3201 FIZIK KEADAAN PEPEJAL
Therefore


where z is the number of nearest neighbour. Define the
Madelung constant as

|
|
.
|

\
|

|
|
.
|

\
|
= =
j
ij
j
ij i
R p
q R
z U U
2
'
1
exp

=
j
ij
p
1
o
R
q R
z U U
j
ij i
2
'
exp
o

|
|
.
|

\
|
= =

PHY 3201 FIZIK KEADAAN PEPEJAL

The total energy of the crystal is given by
U
total
=(2NU
i
)
N is the total number of molecules. The number of
ions is 2N. The term occurs because we must count
each pair of interaction only once. Therefore


|
|
.
|

\
|
= =

R
q
e z N NU U
R
i total
2
/
o

PHY 3201 FIZIK KEADAAN PEPEJAL
To calculate the equilibrium distance between the
nearest neighbors, we use the fact that the derivative
dU/dR=0
|
|
.
|

\
|
= =
=
= +

0 0
2
0
2
2
0
2
2
/ 2
0
2
0
2
/
1
0
0
0
R R
Nq
R
Nq
R
q N
U
z
q
e R
R
q
e
z
total
R
R
o o o

o
o

R
q R
z U U
j
ij i
2
'
exp
o

|
|
.
|

\
|
= =

PHY 3201 FIZIK KEADAAN PEPEJAL

Evaluation of Madelung
constant
Example- a one-dimensional lattice of ions of
alternating sign as shown in the Figure below

R
2, 2ln =
(

+ + + = ....
5
1
4
1
3
1
2
1
1 2 o
In this case


where we took into account the logarithm expansion into
series
( ) ( )

= +
2
1
1 1 ln
n
n
n
n
x
x
PHY 3201 FIZIK KEADAAN PEPEJAL
The cohesive energy for NaCl can be estimated by using
=1.75, R
o
=a/22.8 Angstrom, q=e, =0.1R
o

This implies that the ionic bond is very strong.
Experimentally, this strength is characterized by the
relatively high melting temperatures. For example, the
melting temperature of NaCl is about 1100
o
, while the
melting temperatures for the Na metal is about 400
o

( )
eV -8 eV~ ~
|
|
.
|

\
|
~ 09 . 27
6
8 . 1 1 . 0
1
/
0
0
0
2
0
0
R
R
a
e
a R N
U
o
o
PHY 3201 FIZIK KEADAAN PEPEJAL
Covalent bonding
The covalent bond between two atoms is
usually formed by two electrons, one from
each atom participating in the bond.
The electrons forming the bond tend to be
partly localized in the region between the
two atoms joined by the bond.
Normally the covalent bond is strong: for
example, it is the bond, which couples
carbon atoms in diamond. The covalent
bond is also responsible for the binding of
silicon and germanium crystals
PHY 3201 FIZIK KEADAAN PEPEJAL
In Covalent bonding, outer s and p electrons are
shared between two atoms to obtain noble gas
configuration.
Takes place between elements
with small differences in
electronegativity and close by
in periodic table.
In Hydrogen, a bond is formed between 2 atoms
by sharing their 1s
1
electrons


H + H
H H
1s
1
Electrons
Electron
Pair
Hydrogen
Molecule
H H
Overlapping Electron Clouds
PHY 3201 FIZIK KEADAAN PEPEJAL
The binding of molecular hydrogen
The strongest binding occurs when the
spins of the two electrons are antiparallel
This spin-dependent coulomb energy is
called the exchange interaction.
PHY 3201 FIZIK KEADAAN PEPEJAL
PHY 3201 FIZIK KEADAAN PEPEJAL
In case of F
2
, O
2
and N
2
, covalent bonding is
formed by sharing p electrons
Fluorine gas (Outer orbital 2s
2
2p
5
) share one p electron
to attain noble gas configuration.



Oxygen (Outer orbital - 2s
2
2p
4
) atoms share two p
electrons



Nitrogen (Outer orbital - 2s
2
2p
3
) atoms share three p
electrons

H H
F + F
F F
H
F F
Bond Energy=160KJ/mol
O + O O O O = O
N + N
Bond Energy=54KJ/mol
N N N N
Bond Energy=28KJ/mol
PHY 3201 FIZIK KEADAAN PEPEJAL
Carbon has electronic configuration 1s
2
2s
2
2p
2








Hybridization causes one of the 2s orbitals
promoted to 2p orbital. Result four sp3
orbitals.

Ground State arrangement
1s 2s
2p
Two filed 2p orbitals
Indicates
carbon
Forms two
Covalent
bonds
1s
2p
Four filled sp
3
orbitals
Indicates
four covalent
bonds are
formed
Covalent Bonding
in Carbon
PHY 3201 FIZIK KEADAAN PEPEJAL
Four sp
3
orbitals are directed symmetrically
toward corners of regular tetrahedron.
This structure gives high hardness, high bonding
strength (711KJ/mol) and high melting
temperature (3550
o
C).
Carbon Atom Tetrahedral arrangement in diamond
Structure of Diamond
PHY 3201 FIZIK KEADAAN PEPEJAL
Comparison of Ionic and
Covalent Bonding
PHY 3201 FIZIK KEADAAN PEPEJAL
Atoms in metals are closely packed in crystal
structure.
Loosely bounded valence electrons are attracted
towards nucleus of other atoms.
Electrons spread out among atoms forming
electron clouds.
These free electrons are
reason for electric
conductivity and ductility
Since outer electrons are
shared by many atoms,
metallic bonds are
Non-directional




Positive Ion
Valence electron charge cloud
Metallic Bonding
PHY 3201 FIZIK KEADAAN PEPEJAL
Hydrogen Bonds
Hydrogen bonding arises because a hydrogen
atom is usually a somewhat positive charged
region of a molecule. This can, by electrostatic
attraction, form a weak bond to a negatively
charged region of another molecule
e.g. the water molecule, H
2
O, the shared
electrons shared between the oxygen and
hydrogen atoms tend to stay closed to the oxygen
atom than the hydrogen atom because of the
electronegativity of oxygen. As a results, oxygen
act as the negative end of the dipole and
hydrogen act as the positive ends.
PHY 3201 FIZIK KEADAAN PEPEJAL
Hydrogen bonds are Dipole-Dipole
interaction between polar bonds
containing hydrogen atom.
Example :-
In water, dipole is created due to
asymmetrical arrangement of hydrogen
atoms.
Attraction between positive oxygen pole and
negative hydrogen pole.

105
0
O
H
H
Hydrogen
Bond
Hydrogen Bonds
PHY 3201 FIZIK KEADAAN PEPEJAL