3a Crystal Binding

3a CRYSTAL BINDING
Chapter 3: Crystal Binding

Kulliyah of Engineering
Dept. of MME
Asst. Prof. Dr. Agus Geter
3a.1
Introduction
 What holds a crystal together?

 The attractive electrostatic interaction between the negative
charges of the electrons and the positive charges of the
nuclei is entirely responsible for the cohesion of solids.
 Magnetic forces have only a weak effect on cohesion.
 gravitational forces are negligible.
 Specialized terms categorize distinctive situations:

exchange energy, van der Waals forces, and covalent
bonds.

Dept. of MME
3a.2
Introduction (Cont.)
Figure 1 The principal types of crystalline binding. In (a) neutral atoms with closed electron shells are bound
together weakly by the van der Waals forces associated with fluctuations in the charge distributions. In (b)
electrons are transferred from the alkali atoms to the halogen atoms, and the resulting ions are held together
by attractive electrostatic forces between the positive and negative ions.

Dept. of MME
3a.3
In (c) the valence electrons are taken away from each alkali atom to form a communal electron sea in which
the positive ions are dispersed. In (d) the neutral atoms appear to be bound together by the overlapping parts of
their electron distributions.

Dept. of MME
3a.4
 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 lattice energy (used for ionic crystal) 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.

Dept. of MME
3a.5

Dept. of MME
3a.6
Dept. of MME
3a.7
CRYSTALS OF INERT GASES
 The inert gases form the simplest crystals.
 The electron distribution is very close to that of the
free atoms.
 Their properties at absolute zero are summarized in
Table 4.
 Properties:
 transparent insulators,
 weakly bound, with
 low melting temperatures.
 Outermost electron shell are completely filled.
 Spherically symmetric (distribution of electron charge)
 Holds by van der Waals interaction.

Dept. of MME
3a.8
CRYSTALS OF INERT GASES (Cont.)
Return

Dept. of MME
3a.9
Figure 2 Cubic close-packed (fcc)

crystal structure of the inert gases
Ne, Ar, Kr, and Xe. The lattice
parameters of the cubic cells are
4.46, 5.31, 5.64, and 6.13 A,
respectively, at 4 K.

Dept. of MME
3a.10
 What holds an inert gas crystal together?
 The electron distribution in the crystal cannot be
significantly distorted from the electron
distribution around the free atoms, because the
cohesive energy of an atom in the crystal is only 1
percent or less of the ionization energy of an
atomic electron. Thus not much energy is
available to distort the free atom charge
distributions. Part of this distortion gives the van
der Waals interaction.

Dept. of MME
3a.11
 Van der Waals-London Interaction
 Consider two identical inert gas atoms at a separation R
large in comparison with the radii of the atoms.

 If the charge distributions on the atoms were rigid, the
interaction between atoms would be zero, because the

electrostatic potential of a spherical distribution of
electronic charge is canceled outside a neutral atom by the
elec-trostatic potential of the charge on the nucleus.
 Then the inert gas atoms could show no cohesion and
could not condense. But the atoms induce dipole moments

in each other, and the induced moments cause an
attractive interaction between the atoms.

Dept. of MME
3a.12
 Van der Waals-London Interaction (Cont.)

Dept. of MME
3a.13

Dept. of MME
3a.14
The attractive interaction, ΔU (= the zero point energy of

the system – the energy of the strongest optical absorption)
varies as the minus sixth power of the separation of the two
oscillators.

Dept. of MME
3a.15
 known also as the London interaction or the induced
dipole-dipole interaction.
 It is the principal attractive interaction in crystals of inert
gases and also in crystals of many organic molecules.

 An approximate value of A for identical atoms
is given by
where is the energy of the strongest

optical absorption line and a is the electronic-
polarizability

Dept. of MME
3a.16
Dept. of MME
3a.17
 Repulsive Interaction
 As the two atoms are brought together their
charge distributions gradually overlap (Fig. 4),
thereby changing the electrostatic energy of the
system.
 At sufficiently close separations the overlap energy
is repulsive, in large part be-cause of the Pauli
exclusion principle:
 The elementary statement of the principle is that two
electrons cannot have all their quantum numbers equal.

Dept. of MME
3a.18
Figure 4 Electronic charge distributions overlap as atoms approach. The

solid circles denote the nuclei.

Dept. of MME
3a.19
 Repulsive Interaction (Cont.)

 The Pauli principle prevents multiple
occupancy, and electron distributions of
atoms with closed shells can overlap only if
accompanied by the partial promotion of
electrons to unoccupied high energy states
of the atoms.

Dept. of MME
3a.20

Dept. of MME
3a.21
 Experimental data on the inert gases can be
fitted well by an empirical repulsive potential of
the form B/R12, where B is a positive constant.
 It is usual to write the total potential energy of
two atoms at separation R as (is known as the
Lennard-Jones potential)

Dept. of MME
3a.22
Figure 6 Form of the Lennard-Jones

potential which describes the interaction
of two inert gas atoms. The minimum
occurs at R/s = 21/6 =1.12. Notice how
steep the curve is inside the minimum, and
how flat it is outside the minimum.
The value of U at the minimum

is -e; and U = 0 at R = s.

Dept. of MME
3a.23

 -dU(R)/dR = the force between two atoms.
 Other empirical forms for the repulsive
interaction are widely used, in particular
the exponential form
l exp(-R/r) for other non gas phase materials
where l and r (a measure of the range of
the interaction) are empirical parameters.

Dept. of MME
3a.24
 Equilibrium Lattice Constants
 If the kinetic energy of the inert gas atoms is
neglected, the cohesive energy of an inert gas
crystal is given by summing the Lennard-Jones
potential over all pairs of atoms in the crystal.
For N atoms in the crystal:
where pijR is the distance between reference atom i and any other atom j,
expressed in terms of the nearest neighbor distance R. The factor ½ occurs
with the N to compensate for counting twice each pair of atoms.

Dept. of MME
3a.25
 Equilibrium Lattice Constants (Cont.)
 If the equilibrium value R0 is given by requiring
that Utot (total energy of the crystal) be a
minimum with respect to variations in the
nearest neighbor distance R, it can be predicted
the lattice constant of the crystal.
 The observed values of R0/s using the
independently determined values of s given in
table 4, are:

Dept. of MME
3a.26
 Cohesive Energy (Cont.)
 The cohesive energy of inert gas crystals at absolute
zero and at zero pressure is obtained.
Consider for fcc structure
then
And, at R = R0
then

Dept. of MME
3a.27
Dept. of MME
3a.28

3a Crystal Binding

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3a CRYSTAL BINDING

Chapter 3: Crystal Binding

 What holds a crystal together?

 Specialized terms categorize distinctive situations:

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

 The lattice energy (used for ionic crystal) is

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Figure 2 Cubic close-packed (fcc)

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

large in comparison with the radii of the atoms.

interaction between atoms would be zero, because the

could not condense. But the atoms induce dipole moments

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

The attractive interaction, ΔU (= the zero point energy of

Chapter 3: Crystal Binding

gases and also in crystals of many organic molecules.

where is the energy of the strongest

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Figure 4 Electronic charge distributions overlap as atoms approach. The

Chapter 3: Crystal Binding

 Repulsive Interaction (Cont.)

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Figure 6 Form of the Lennard-Jones

The value of U at the minimum

Chapter 3: Crystal Binding

 Repulsive Interaction (Cont.)

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Chapter 3: Crystal Binding

Consider for fcc structure

Chapter 3: Crystal Binding

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