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Bonding in Crystals
Dr. rer. nat. Muldarisnur
Cl Na NaCl
2A 3A 4A 5A 6A 7A
Force between the atoms is the negative of the slope of this curve. At
equlibrium, repulsive force becomes equals to the attractive part.
Solid State Physics Dr. rer. nat. Muldarisnur 7
The potential energy of interatomic interaction
repulsive
V(r) Repulsive force a Pauli exclusion principle prevent
the crystal from collapsing
Attractive force a bonding hold atoms together to
form solid
equilibrium distance
r
Distance between
two atoms
Types of bonding:
attractive 1. Ionic bonds
2. Covalent bonds
V (r ) 3. Metallic bonds
Interatomic force F (r )
r
4. Van der Waals
V
equilibrium distance 0 5. Hydrogen
r r r0
a b
or simply: V (r ) m n
r r
250
200
Argon gas
12 6 150
4
v(r)/kb (K)
100
U LJ
r r 50
0
0.3 0.5 0.7 0.9 1.1 1.3 1.5
-50
-100
-150
r (nm )
12
6
u r 4
LJ
r r
H2 2.7 4
Ar 3.2 15
N2 3.7 13
CO2 4.5 40
ε
repulsion dispersion (van der Waals)
Multiple atoms - 12 6
a E 4
assume pairwise
i j R ij
R
1 2 3 ij
additive:
b Isomers
1 3 2 • different minima on potential energy surface
• number of isomers grows exponentially
with # of atoms
c • a and b – permutation-inversion isomers
• Ea = Eb ≠ Ec
Solid State Physics Dr. rer. nat. Muldarisnur 14
Chemical Bond
Types of Chemical Bond: Ionic and Covalent
Inoinzation energy: the energy required to remove an electron from a
neutral isolated atom to form an ion with one positive charge
Electron affinity: the amount of energy released when an electron is
added to a neutral isolated atom to form an ion with one negative
charge.
Electronegativity: the average of the first ionization energy and the
electron affinity. It is the measure of the ability of an atom or molecule to
attract electrons in the context of a chemical bond.
Chemical bonding between two atoms is determined by the difference in
electronegativity
Large difference a ionic bonding
e.g. Na-Cl (3.16 - 0.93 = 2.23)
Small difference a covalent bonding
e.g. C-O (3.44 – 2.55 = 0.89)
O-O (0)
Solid State Physics Dr. rer. nat. Muldarisnur 15
Electronegativity vs Bond Type
The binding energy of the atoms in all solids results from the reduction in
energy of atomic electrons due to the proximity of the neighboring atoms
Dipole - dipole
Polar Non Polar
Dipole – non dipole
Ionic : Electrostatic
attraction between ions.
Covalent : Sharing of
electrons.
Na Cl
Kapustinskii equation :
U0 = (1210 kJ Å / mol) * (n zA zB / d0) * (1 – (d* / d0))
Where:
e is the charge of the electron, 0 is the permittivity of a vacuum
N is Avogadro’s number
zA is the charge on ion “A”, zB is the charge on ion “B”
d0 is the distance between the cations and anions (in Å) = r+ + r-
A is a Madelung constant
d* = exponential scaling factor for the repulsive term = 0.345 Å
n = the number of ions in the formula unit
Solid State Physics Dr. rer. nat. Muldarisnur 25
Ionic Bonding
The origin of the equations for lattice energies. U0 = Ecoul + Erep
The lattice energy U0 is composed of both coulombic (electrostatic) energies and an additional
close-range repulsion term - there is some repulsion even between cations and anions because
of the electrons on these ions. Let us first consider the coulombic energy term:
In this case the energy of coulombic forces (electrostatic attraction and repulsion) are:
Ecoul = (e2 / 4 0) * (zA zB / d) * [+2(1/1) - 2(1/2) + 2(1/3) - 2(1/4) + ....]
because for any given ion, the two adjacent ions are each a distance of d away, the
next two ions are 2d, then 3d, then 4d etc. The series in the square brackets can
be summarized to give the expression:
Ecoul = (e2 / 4 0) * (zA zB / d) * (2 ln 2)
where (2 ln 2) is a geometric factor that is adequate for describing the 1-D nature of
the infinite alternating chain of cations and anions.
Solid State Physics Dr. rer. nat. Muldarisnur 26
Ionic Bonding
For a 3-dimensional arrangement, the geometric factor will be different for each
different arrangement of ions. For example, in a NaCl-type structure:
Ecoul = (e2 / 4 0) * (zA zB / d) * [6(1/1) - 12(1/2) + 8(1/3) - 6(1/4) + 24(1/5) ....]
The geometric factor in the square brackets only works for the NaCl-type structure,
but people have calculated these series for a large number of different types of
structures and the value of the series for a given structural type is given by the
Madelung constant, A.
This means that the general equation of coulombic energy for any 3-D ionic solids is:
Ecoul = (e2 / 4 0) * (zA zB / d) * A
Note that the value of Ecoul must be negative for a stable crystal lattice.
Solid State Physics Dr. rer. nat. Muldarisnur 27
Ionic Bonding
The numerical values of Madelung constants for a variety of different structures are
listed in the following table. CN is the coordination number (cation, anion) and n is
the total number of ions in the empirical formula e.g. in fluorite (CaF2) there is one
cation and two anions so n = 1 + 2 = 3.
Notice that the value of A is fairly constant for each given stoichiometry and that the
value of A/n is very similar regardless of the type of lattice.
Solid State Physics Dr. rer. nat. Muldarisnur 28
Ionic Bonding
If only the point charge model for coulombic energy is used to estimate the lattice energy (i.e.
if U0 = Ecoul) the calculated values are much higher than the experimentally measured lattice
energies.
E.g. for NaCl (rNa+ = 0.97Å, rCl- = 1.81Å):
This is the Born-Mayer equation, when the constants are evaluated we get
the form of the equation that we will use:
U0 = 1390 (zA zB / d0) * A * (1 - (d* / d0)) in kJ/mol
Note: d* is the exponential scaling factor for the repulsive term and a value
that we will use for this is 0.345 Å.
Solid State Physics Dr. rer. nat. Muldarisnur 29
Ionic Bonding
Using the Born-Mayer equation, for our example with NaCl.
Kapustinskii observed that A/n is relatively constant but increases slightly with coordination
number. Because coordination number also increases with d, the value of A/nd should also be
relatively constant. From these (and a few other) assumptions he derived an equation that does
not involve the Madelung constant:
Kapustinskii equation :
U0 = (1210 kJ Å / mol) * (n zA zB / d0) * (1 – (d* / d0))
One advantage of the Kapustinskii equation is that the type of crystal lattice is not important.
This means that the equation can be used to determine ionic radii for non-spherical ions (e.g.
BF4-, NO3-, OH-, SnCl6-2 etc.) from experimental lattice energies. The self-consistent set of radii
obtained in this way are called thermochemical radii.
Solid State Physics Dr. rer. nat. Muldarisnur 30
Covalent bond
Non-metal elements usually just need one or two electrons to fill their
outer shells. So how do they form a bond?
incomplete
Cl outer shells Cl
The shared electrons join the atoms together. This is called a covalent
bond.
Solid State Physics Dr. rer. nat. Muldarisnur 31
Covalent Bond
When the electronegativity between two atoms is small, the two atoms
can form covalent bond by sharing a pair of electrons (one from each
atom).
e.g. Si, Ge, Diamond, Graphene, carbon nanotube, fullerene
For two atoms with orbital wavefunctions: 1 , 2
The molecular orbital of the two atoms are linear combinations of 1
and 2
b 1 2
a 1 2
H Cl H Cl
Hydrogen and chlorine both need one more electron to fill outer
shells. By sharing one electron each, they both have a stable outer
shell and a covalent bond is formed.
Solid State Physics Dr. rer. nat. Muldarisnur 34
Covalent Bond in water
Compounds can contain more than one covalent bond.
Oxygen (2.6) needs 2 more electrons, but hydrogen [1] only needs
1 more. How can these three elements be joined by Covalent
Bond?
The oxygen atom shares 1
electron with 1 hydrogen
atom, and a second electron O
with another hydrogen H H
atom.
Higher
electronegativity
means greater
electron attraction
to that atom
+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 8e. bonding
-ex: polymer
secondary bonding
+ -
+e -e
+ -
At equilibrium , we have
1
dE nA nm B m
0 ro & E (ro ) 1
mB
m
dr r ro ro n
A B
E (r ) n m
r r
dE nA mB
0 n 1 m 1
dr r ro r r
nA mB mn mB
n 1
m 1 r
r r nA
1
nA nm B m
ro & E (ro ) m n 1
mB ro
–
Hydrogen bond
The slightly positive ends (indicated by
(+) of the water molecules +
dotted line)
become aligned with the – +
–
slightly negative ends (–) of –
+ +
other water molecules.
+
–
Type of material Solid metallic Ceramics and glass Polymers and Helps form solid
formed elements and alloys some polymers
ceramics/glasses
Strength of bond Relatively strong Very strong Very strong Weak
Properties Good conductors, Brittle, Insulators, Help determine a lot
Produced workable, corrode high melt temps, don’t corrode of properties of
easily, generally high nonconductors as solids, covalent compounds
melt temps but don’t corrode (polymers). Soft and
variable plastic
Types of
Bonding
Energy Energy
Bond Type Energy (eV)
(kJ/mole) (kJ/mole)
Ionic ~5-15 (strong) ~500-1500 NaCl: 640
Diamond:
Covalent ~1-10 (strong) ~100-1000
~710
~0.5-8.5
Metallic ~50-850 Fe: 406
(strong)
Hydrogen ~0.05-1.5 ~5-155 H2O: 51
Van der Waals ~0.01-0.5 ~1-50 Ar:7.7
x 2
x 3
x 4
Since ln(1 x) x ... 2 ln 2
2 3 4