Crystal Binding (Bonding) Part IV

Quantitative Models of Ionic Bonding

 Ionic Crystals
• As we’ve already said, these consist of atoms with
Large Electronegativity Differences
Most naturally occurring minerals are ionic crystals.
Further, many of these minerals are oxides.
• As we’ve already said, a first approximation is
that these oxides can be thought of as an array of
oxygen atoms in a close packed arrangement,
with metallic ions fitting into interstitial sites
between the oxygens. Most of these crystals are
not very useful to physicists. But, some Geoscience
friends are experts on these kinds of crystals.
 Ionic Bonding
• This bonding occurs between atoms with Large
Electronegativity Differences. This means that the
2 atoms are usually far removed from each other
in the periodic table. This also means that they can
easily exchange electrons & stabilize their outer
electron shells (which become more inert gas-
like). So, electronically neutral bonds between cations
(positive ions) & anions (negative ions) are created.
Example: NaCl
Na (1s22s22p63s1) Na+ (1s22s22p6) + e-
Cl (1s22s22p63s23p5) + e- Cl- (1s22s22p63s23p6)
 Ionic Bonding
Example: NaCl
l
Na (1s22s22p63s1) Na+ (1s22s22p6) + e-
Cl (1s22s22p63s23p5)+e- Cl (1s22s22p63s23p6)
 Physical Properties of Ionic Materials
In general, Ionic Materials:
•Are harder than metals or molecular solids, but
softer than covalently bonded materials.
•Have greater densities than metals or molecular
solids, but are less dense than covalently bonded solids.
•Have low electrical & thermal conductivities in
comparison with most other materials.
•These & other physical properties are caused by
the ionic bond strength, which is related to
1. The spacing between the ions.
2. The ionic charge.
 Melting Points of Ionic Materials
Decrease with Increasing Interionic Distance
9
17
35
53

Sodium with various

anions
12
20
+2 38
56
cations

+1 3
cations 11
19
37
 Mechanical Hardness of Ionic Materials
Decreases with Increasing
4 Interionic Distance

12

20

38 56

22

21

12

11
 Atomic & Ionic Radii
In Quantum Mechanics, the concepts
“Atomic Radius” &
“Ionic Radius”
ARE NOT WELL-DEFINED!
• Electrons are waves & are spread out
over the atomic volume with no rigid
“boundary” that is the “atomic radius”.
• However, sometimes in crystalline
solids, these concepts can be useful.
In Quantum Mech, “Atomic Radius” &
“Ionic Radius” Aren’t Well-Defined!
• Sometimes, these concepts can be useful to
obtain a qualitative (sometimes even close to
quantitative!) understanding of interatomic
(inter-ionic) distances (bond lengths), as well
as certain other material properties.
• How these radii are defined is certainly not
rigorous & varies from one bond type to
another, sometimes from one material to another
& sometimes from one application to another.
• The Atomic Radius of a neutral atom
can be crudely thought of as the Mean
Quantum Mechanical Radius <r> of
the orbital of the outer valence electron
for that atom.
• Similarly, the Ionic Radius of an ion
can be crudely thought of as the Mean
Quantum Mechanical Radius <r> of
the orbital of the outer valence electron
for that ion.
• In quantum mechanics, <r> could be
calculated using the wavefunction
(solution to Schrödinger’s Equation)
of the relevant valence electron.
However, this quantum mechanical
calculation is almost never done.
Instead, these radii are most often
treated as parameters which are
obtained from crystal structure data.
• For example, one means to find an Ionic
Radius for a metallic ion is to obtain it
from data on the crystalline solid for that
metal. In this case, the Ionic Radius
would be half the ion-ion bond length:
rI = (½)d
(d = bond length or nearest neighbor distance)
• As an example, take the copper ion Cu+.
The lattice structure of Cu metal is FCC.
X-ray data gives d100 = a = 3.61 Å.
 rI = (½)d
(d = bond length or nearest neighbor distance)
• The copper ion Cu+. The lattice structure of Cu
metal is FCC. See figure. X-ray data gives
d100 = a = 3.61 Å
• From the figure, near neighbor distance = (½)(2a2)½

a
⇒ Cu+ Ionic Radius
= (¼)(2a2)½ = 1.28 Å.
a Note: The Cu+ ionic radius is
different than the radius of the
Cu++ ion. It is also different in the
covalently bonded material CuO2.
• The Atomic (or Ionic) Radius of a
given atom (or ion) can be different,
depending on the material of interest.
• For example, for atom X, this radius depends on:
1. The crystal structure of the material that X is in.
2. The coordination number (# nearest- neighbors)
for X in that material.
3. The bond type.
4. The % of ionic or covalent character of that
bond.
5. .....
 Variation of the Atomic Radius with
Position in the Periodic Table
1. It increases from top to bottom down a column.
(This is what I called a “Chemical Trend” earlier)
• Why? Going down a column, the energies of valence
electrons increase, so their binding energy with the
nucleus gets weaker moving down the column. They
are not bound as tightly to the nucleus as the electrons
in the filled shells because they are screened or shielded
(pushed away) by other electrons in inner levels.
2. It decreases from left to right in a row.
• Why? The number of protons in the nucleus increases
to the right. This pulls electrons closer to the nucleus
going from left to right.
The Periodic Table & Atomic Radii
Atomic Radius vs. Atomic Number
Nuclear charge increases
Shielding increases
Atomic radius increases
Ionic size increases
Ionization energy
decreases
Electronegativity decreases
Summary
Shielding is constant

Nuclear charge increases

Atomic Radius decreases

Electronegativity increases
Ionization energy increases
 Atomic Radius
• The overall trend in atomic radius looks like this.
 Ionic Radii
• Metallic Elements easily lose electrons.
• Non-Metals more readily gain electrons.

How does losing or gaining

an electron effect the
radius of the atom (ion)?
 Positive Ions
• Positive ions are always smaller than
the neutral atom, due to their loss of
one or more outer shell electrons.
 Negative Ions
• Negative ions are always larger than
the neutral atom due to the fact that
they’ve gained electrons.
 Ion size Trends in Rows.
• Going from left to right, there is a
decrease in size of positive ions.
• Starting with group 5, there is sharp
increase followed by a decrease in
the size of the anion as you move
from left to right.
 Ion size Trends in Columns

• Ion size increases going

down a column for both
positive and negative ions
 Covalent Radii
• Obviously, this applies to atoms in a
covalently bonded material.
In a pure elemental solid, the
Covalent Radius is simply half of
the bond length.
• Once that is found for a given atom, then
the covalent radius of that atom is assumed
to be the same in any material in which that
atom participates in a covalent bond.
 Charged Systems
• How are charged systems (like ions) handled?
• In the early days of solid state physics, this
was a difficult problem.
• Why? Because the Coulomb potential is long-
ranged! That is, in principle, the Coulomb
potential due to a given (+ or -) ion extends all
the way out to r ∞
To do calculations, people often treat the
Coulomb potential as if it were a
short-ranged potential:
 Approximation:
The Coulomb potential is short-ranged:
• In practice, cutoff the potential at r > (½)L.
L is empirically determined. Problem:
• The effect of the discontinuity never disappears:
(1/r) (r2) gets bigger as r gets bigger!
• An Image Potential solves this:
VI = Σn v(ri-rj+nL)
• But this summation diverges!
27
 Model 1-D Madelung Sum:
• Consider a Model Ionic Lattice in 1
Dimension, as in the figure.
… -– + -– + -– + -– + …
R

• The value of α is defined in terms of the lattice constant

R. Start on a negative ion, summing (left & right)
• This sum is conditionally convergent! This
means the order of the terms in the sum matters!
 Model Ionic Lattice in 1 Dimension
… -– + -– + -– + -– + …
R

The value of α is defined in terms of the lattice constant

R. Start on a negative ion, summing (left & right)
This sum is conditionally convergent! This means the order of the
terms in the sum matters!
• Since ionic crystals involve more than 2 ions,
the attractive & repulsive forces between
neighboring ions, next nearest neighbors, etc.,
must be considered.
• The Madelung Constant is derived for each
type of ionic crystal structure. It is the sum of
a series of numbers representing the number of
nearest neighbors & their relative distance from
a given ion.
• The Madelung Constant is specific to the
crystal type (unit cell), but independent of
interionic distances or ionic charges.
 3-D Madelung Sums
• In 3D this series presents greater difficulty.
The series will not converge unless successive
terms in the series are arranged so that + and
terms nearly cancel.
Powerful methods were developed by Ewald (Ann. Physik 64, 253
(1921)
Evjen (Phys. Rev. 39, 675 (1932) and Frank (Phil. Mag. 41, 1287
Results for some Lattices:
(1950) .

Velectrostatic ~ α/R
Lattice
NaCl α = 1.747565
CsCl α = 1.762675
ZnS α = 1.6381 31
 Long-Ranged Potentials
• Why not make the potential long ranged? To answer this, consider
a cubic lattice with only +1 charges, & its Coulomb potential.

• The approximate integral diverges!

Correct! A charged system with
infinite
charge has infinite potential.
• Consider instead a cubic lattice with
charge neutrality, i.e. with ±1 charges.

• Again, we need a convergent lattice sum.

– Energy is finite in a charge neutral cell
 What is a Long-Ranged Potential?
• A potential is long-ranged if the real-space
lattice sum does not (naively) converge.
• In 3d, a potential is Long-ranged if it
converges at rate < r–3.
• In 2d, a potential is Long-ranged if
converges at rate < r–2.
• In practice, we often use techniques for
potentials that are not strictly long-
ranged.
 What is a Long-Ranged Potential?
MOTIVATION for this bothersome math?
Most interesting systems contain charge!
• Any atomic system at the level of electrons
and nuclei.
• Any system with charged defects (e.g.,
Frenkel defects)
• Any system with dissolved ions (e.g.
biological cases)
• Any system with partial charges (e.g.
chemical systems)
In general, Total Lattice Energy =
Ion-pair energy ×
Madelung constant M (α)
Crystal Structure Madelung Constant
NaCl 1.748
CsCl 1.763
Zinc blende 1.638
Wurtzite 1.641
Fluorite 2.519
Rutile 2.408
Origin of the Madelung Constant
The Madelung Series does not converge:
However, a concentric cube calculation
does converge:
 What decides the shape an ionic lattice takes?
Ionic Solids can be thought of as anion structures with
cations filling cavities (holes) between the anions.
• Bonding is strongest with the most cation-anion
interactions that do not crowd the anions into each other
(which is the same as leaving gaps between anions and
the cation.)
 What decides the shape an ionic lattice takes?
• At the “stability limit” the cation is touching all the
anions and the anions are just touching at their edges.
Beyond this stability limit the compound will be
stable.
Ionic charge has
a huge effect on
the lattice energy.
 Madelung Constants
Crystal Madelung
Structure Constant
Cesium Chloride 1.763
Fluorite 2.519
Rock Salt (NaCl) 1.748
Sphalerite 1.638
Wurtzite 1.641