Bonding in Solids

Outline
1. Ionic bonding • Ions, ionic radii
• Ionic structures
• Lattice energy of ionic crystal
• Born-Haber cycle

2. Partial covalent bonding • Coordinated polymeric structures

• Bond valence and bond
• Non-bonding electron effects

3. Metallic bonding • Band theory

• Band structure of metals, insulators and
semiconductors
• Band structure of inorganic solids
 Bonding

General idea:

• Mixed bonding type: Ionic, covalent, van der Waals, and

metallic e.g. TiO and CdI2
• Ionic bonding: high symmetry with the highest possible
coordination number (larger lattice energy)
• Covalent bond: directional, prefer a certain coordination
environment
• Position in periodic table… high valency vs. low valency
Ionic Bonding
 Ionic Bonding
What’s the size of ions in crystals?
Several models have been established for the calculation of ionic radii e.g.
Pauling, Goldschmidt.. Shannon and Prewitt

http://www.crystalmaker.com/support/tutorials/crystalmaker/AtomicRadii.html
 Ionic Bonding
High quality X-ray diffraction: electron density contour map

• Ions are spherical

• Central core + outer sphere of
shell
• Ions are charged, elastic and
polarizable
•Assignment of radii is difficult…
lead to the variation of reported
values
• Flexibility in ionic radii,
depends on coordination
environment
LiF
 Ionic Radii
Trend in ionic radii:

• Radii increase with atomic number

for any vertical group (s and p-block
elements)
• Isoelectronic series of cations, radii
decrease with increasing charge

• Cation radius decrease with

increasing oxidation state
• Cationic radius increase with
increasing coordination number
• Lanthanide contraction (d and f
block elements)

• Transition vs. main group

• Diagonal ion have similar ionic size

 Ionic Structure_General Principles
• Ions are charged, elastic and polarizable spheres
• Ionic structures are held by electrostatic force
• Highest coordination numbers (to maximize the electrostatic
attraction between ions, lattice energy)
• Reduced nearest neighbor repulsive interaction (high symmetry
and maximized volume)
• Local electroneutrality
 Local Electroneutrality
Electrostatic valence rule:
The charge of a particular ion must be balanced by equal and opposite
charge on the immediately surrounding ion

Electrostatic bond strength (ebs) of cation-anion bond:

For cations Mm+ surround by n anions : ebs = m/n

For anions Ox-: Sum of m/n = ∑ ebs = x

For example: MgAl2O4, structure

1. Explain the structure with O

bond strength
Mg
2. Predict the polyhedral
linkage
Al
 Radius Ratio Rule
• Cation must be in contact with its anionic neighbors. (lower limit
on cation size)
• Neighboring anions may or may not be in contact

Octahedral cation site (6CN):

(2rx)2 + (2rx)2 = [2(rM + rx)]2

2rx(√ 2) = 2(rM + rx)

rM/rx = (√ 2) – 1 =
0.414
Ratio of Rcation / Ranion

> 0.414 cation push the anions apart,

occupy a site of larger CN
< 0.414, occupy a site of smaller CN (not
stable, rattle inside the anion polyhedron)
Minimum rM/rx of Cubic and Tetrahedral Structures

Cubic (8CN) Tetrahedral (4CN)

2(rM + rx) = cube body diagonal 2rx = face diagonal

a = 2rx (2rx)2 + (√ 2rx)2 = [2(rM + rx)]2

2(√ 3)rx = 2(rM + rx) rx(√ 6) = 2(rM + rx)

rM/rx = (√ 3) – 1 = rM/rx = [(√ 6) – 2]/2 = 0.225

0.732
 Predicting Trends in CN
Radius ratio rules: qualitative guide only

Borderline case:
1. Polymorphs: contains both tetrahedral and
octahedral

2. Distorted structure: BaTiO3, the

reversible displacement of Ti in an applied
electric field, lead to Ferroelectrictiy
 Electrostatic Forces

Ionic structure: hold together by electrostatic forces (electrostatic

repulsion and attraction in crystal)

Lattice energy U, is the net potential energy of the arrangement of

charges that forms the structure.

NaCl(s) → Na+(g) + Cl-(g)

ΔH = U

Coulomb’s Law:

F = Z+Z-e2/r2 Distance
between the ions r
Attractive Electric charge
force
Charge
Mz+ Xz-
on the
ions
Lattice Energy of Ionic Crystals

Coulombic potential energy:

Distance
V = -(Z+Z-e2)/r between the ions

Charge on Electric charge

the ions

Born repulsion energy:

In the range
V = B / rn of 5 to 12

constant Distance
between the ions

Attraction “-” and Repulsion “+”

 Determination of Lattice Energy
Lattice energy is calculated by combining the net electrostatic attraction
and the Born repulsion energies and finding the internuclear separation,
which gives the maximum U value.
Coulombic potential energy
For example: NaCl
V1 = -6(Z+Z-e2)/r
V2 = 12(Z+Z-e2)/√2r
V3 = -8(Z+Z-e2)/√3r
V = [-(Z+Z-e2)/r][6-(12/√2)+(8/√3)-(6/√4)… ]

V = -(Z+Z-e2)NA/r

Madelung constant A, depends on crystal structure

Lattice energy: U = -(Z+Z-e2)NA/r + BN/rn

dU/dr = 0, U = [-(Z+Z-e2)NA/re](1-
1/n)
 Determination of Lattice Energy

More precisely: • Born repulsive term is Be(-r/ρ)

• Zero point vibration (2.25Nhν)
• van der Waals dipole interactions (-NC/r6)

Complete equation for U:

U = -(Z+Z-e2)NA/re + BNe-r/ρ - NC/r6 + 2.25Nhν

(N, A, B, e, hν are constant for a particular structure)

U of divalent ions >> monovalent ions (about 4 times)

 Kapustinskii’s Equation
When CN increase, Madelung constant A and re increase, the effect
are proposed to be auto-compensated
(substitute ρ=0.345, A=1.745
U = [-(Z+Z-e2)NA/re](1 - ρ/re) and values for N and e)

U = [1200.5V(Z+Z-)/(rc + ra)][1 – 0.345/(rc + ra)]

re = rc + ra, V = number of ions per formula

To predict the stable existence of several unknown compounds and the

values for ionic radii
 Born-Haber Cycle
Lattice energy of ionic crystal is equivalent to its heat of formation,
which can not be measured experimentally.

Na+(g) + Cl-(g) → NaCl(s) ΔH = U

However, heat of formation can be measured relative to the reagents

in their standard states.
ΔHf
Na(s) + ½ Cl2(g) NaCl(s) ΔH = ΔHf
½D U
EA
S Cl(g) Cl-(g) + Na+(g)

IP
Na(g)

Hess’s Law ΔHf = S + ½ D + IP + EA + U

 Uses of Born-Haber Cycle
• Check the internal consistency of data
• Predict the unknown data
• Estimate the stability of unknown compound
• Evaluate the bonding (ionic vs. covalent)
• Crystal field stabilization energies of transition metals

Stability of compound: ionization potentials, lattice energies and

the relative stability of elements in different oxidation states

e.g. MgCl vs. MgCl2

Covalent Bonding
 Partial Covalent Bond
The outer electronic charge density on an anion is polarized
towards and by neighboring cation. There is some overlapping of
electron density.

For example: AlF3 > AlCl3 > AlBr3 > AlI3

A transition from ionic to covalent bond as electronegativity

difference between two elements decrease

How to quantify the degree of covalent character?

Sanderson’s Method:
Regards all bonds in non-molecular structures as polar covalent.
The value of partial charges on an atom can be estimated using a
scale of electronegativity. The charge on the atom is ±1 in pure
ionic structure.
 Effective Nuclear Charge
The positive charge that would be felt by a foreign electron on
arriving at the periphery of the atom.
Valence electron are not effective in screening/shielding the outside
world from the positive charge on the nucleus.

Ionization potential, electron affinity and electronegativity

increase, atomic radii decrease
Atomic Radii

• Ionic radii is controversial

• Non-polar covalent bond can
be measured accurately

Partial
r = rc - Bδ
charge

Non-polar constant
covalent bond

Cation: smaller radii (nuclear

charge unchange, valence
electrons are removed)
Anion: larger radii
 Electronegativity
The electronegativity of an atom is a measure of the net attractive
force experienced by an outermost electron towards nucleus

S = D/Da Electron density that would be

expected for the atom by linear
interpolation of the D values for the
Electron density of the atom inert gas elements
(atomic number/atomic volume)

Principle of electronegativity equalization:

When two or more atom initially different in electronegativity combine

chemically, they adjust to have the same intermediate electronegativity
within the compound
Sb = (S1S2)1/2

For example, NaF Sb = (SNaSF)1/2

= (0.7×5.75)1/2
= 2.006
Determination of Partial Charge and Atomic Radii
Partial charge δ is the ratio of change in electronegativity undergone
by an atom on bond formation to the change it would undergone on
becoming completely ionic with charge + or -1

1. ΔS = S - Sb
δ = ΔS/ΔSc
2. ΔSc = 2.08(S)1/2

Example BaI2: SBa = 0.78 SI = 3.84

Intermediate electronegativity = Sb = (SBaSI2)1/3 = 2.26

ΔSBa = 2.26-0.78 = 1.48; ΔSI = 3.84-2.26 = 1.58

ΔSc = 1.93 (Ba); 4.08 (I)

δ = ΔS/ΔSc = 0.78 (Ba); -0.39 (I)

rBa = rc – Bδ = 1.70 Å; rI = rc – Bδ = 1.87 Å

Ba-I distance = 1.70 + 1.87 = 3.57 Å
 Mooser-Pearson Plots
Mooser-Pearson Plots is good for predicting the structure based on
covalent character of bonds

•Quantum number n
•Difference in electronegativity

Four structural categories:

Zinc blende, wurtzite, rock salt and CsCl

Bonding Structure
 Philips-Van Vechten Ionicity

Optical absorption spectra of AB compounds Î Eg (band gap)

For isoelectronic series of compounds, the bandgaps have contributions

from: (a) homopolar bandgap, Eh and (b) a charge transfer C

Eg2 = Eh2 + C2

Ionicity (fi): ionic character in bonds = C2/Eg2

(C = 0 in homopolar covalent bond, and C = Eg in pure ionic bond)

Δx (Mooser-Pearson) ~ C (Philips)
n (Mooser-Pearson) ~ Eh (Philips)

A theoretical support for Mooser-Pearson Plots

 Valence Bond Theory
Valence bond theory is developed for molecular materials

Ionic bond Covalent bond

1. Electrostatic bond strength (ebs) Bond valence (bv)

2. Formal charge of anion Valence of the atom

Valence sum rule:

Valence of a atom (Vi) = sum of bond valence between atom

and neighboring atom (∑bvij)

• To check on the correctness of a proposed

bv inversely correlate structure
with bond length
• To locate hydrogen atom in X-ray
crystallography studies
• To distinguish isoelectronic atom Al3+ and
Si4+ position in aluminosilicate structure
 Non-bonding Electron Effects
In transition metal compounds, the majority of the d electrons on
the metal atom do not usually take part in bond formation but do
influence the coordination environment

Crystal Field Theory

http://wwwchem.uwimona.edu.jm:1104/courses/CFT.html
 High Spin vs. Low Spin State

Low spin, Δ > P High spin, Δ < P

The magnitude Δ depends on ligand (strong vs. weak field) and

also the metal (which row, 5d > 4d > 3d). It is set equal to 10Dq.

Crystal field stabilizing energies (CFSE), leads to increase lattice

energy. d0, d5 and d10 do not exhibit CFSE.
Radii in Octahedral Coordination

• d0, d5 and d10: spherically symmetrical

• Electrons in t2g orbital do not shield the bonding electron
from this extra charge (geometry), while electron in Eg do
shielding the nuclear charge.
 Jahn-Teller Distortions
• For those ions with not equally occupied Eg orbital, e.g. d9, d7
(LS) and d4 (HS).
• The Eg orbital is no longer degenerate since metal ion is not a
free ion but is octahedrally coordinated.
• Doubly occupied Eg orbital experience stronger repulsion will
lengthen the metal-ligand bond that leads to a lowering of energy.
 Other Coordination Modes
Tetrahedral
Other coordination structures

• None of the d-orbitals point directly

toward ligands
• dxy, dxz, dyz are closer to the ligand
than other two orbitals
 Octahedral vs. Tetrahedral
e.g. Cr3+ (d3) Octahedral coordination: 1.2 Δoct
Tetrahedral coordination: 0.8 Δtet
The values of CFSE may be used to predict site preferences.

Coordination preference: Spinel structures (AB2O4)

• Normal (A-tetrahedral, B-octahedral; A = M2+, B = M3+)

• Inverse (A-octahedral, B-tetrahedral and octahedral; A = M4+, B = M2+)
• Intermediate between normal and inverse
 Lone-pair Effect

For post transition elements

e.g. Pb2+ (4f145d106s2)

Ions are repelled by the lone Î bond lengthen

Metallic Bonding
 Metallic Bonding and Band Theory
• Metal has delocalized valence electrons
• Metallic bonding is the bonding between atoms within metals. It
involves the delocalized sharing of free electrons among a lattice of
metal atoms

Chemical approach: molecular orbital theory

Overlap of MOs, delocalized Formation of energy level

over both atoms (delocalized over all atoms in crystal)
 Band Structure

For example, Na (1s22s22p63s1):

3s and 3p bands are overlapped at interatomic distance r0,

valence electron 3s1 is not confined in 3s band.
 Physical Approach to Band Theory

Free electron theory

• Fermi level: the highest filled level at absolute zero

• Work function: the energy required to remove the uppermost
valence electrons from the potential wall

Density of states N(E)

 Refined Band Theory
Potential inside the crystal is regarded as periodic

So the uninterrupted continuum of energy levels does not occur, only

certain bands of energies are permitted for electrons

In some materials, band overlap occurs, in others, a forbidden gap

exists.
 Band Structure of Metals
Valence band is part full, electrons in singly occupied states close
to Ef are able to move

Overlapping of s and p valence bands

Band Structure of Insulators and Semiconductors

Band structure of insulators Band structure of semiconductors

• Valence band is full • Valence band is full

• Large forbidden gap from next • Small forbidden gap from next energy
energy gap, e.g. 6eV gap, e.g. 0.5 – 3.0eV

• Very small amount of electron can • (intrinsic semiconductors) number of

be promoted to empty conduction electrons in the conduction band is
band governed by magnitude of bandgap and
temperature
 Band Structure of Inorganic Structures
1. III-V, II-VI and I-VII compounds

e.g. NaCl Na+: 1s22s22p6

Cl-: 1s22s22p63s23p6

Empty cation orbitals will form conduction band, and full anion
orbitals will form valence band

Promotion of a electron from valence band to conduction band is

may be regarded as back transfer of charge from Cl- to Na+.
Therefore, the magnitude of the bandgap is correlated to the
difference in electronegativity between anion and cation.

Eg2 = Eh2 + C2 Ionic energy

Homopolar bandgap
 Band Structure of Inorganic Structures
2. Transition metal compounds

In some case, partly filled metal d-orbitals could overlap to form d bands

General guidelines:
a. The formal charge on the cation is small
b. The cation occurs early in the transition series
c. The cation is in the second or third transition series
d. The anion is reasonably electropositive

Examples please refer to book p. 120

Also related to crystal structure:

For example: Fe3O4 (inverse spinel) vs. Mn3O4 (normal spinel)

[Fe3+]tet[Fe2+, Fe3+]octO4 [Mn2+]tet[Mn3+2]octO4

 Band Structure of Inorganic Structures
3. Fullerenes and graphite

Overlap of π−π orbitals,

delocalization of π electrons

Graphite:
• infinite layers of benzene molecules
• π−π* orbitals overlap by about 0.04eV in the 3D graphite structure
 Fullerene (C60)

• Narrower valence and conduction band

• Bandgap is 2.6eV
• C60 able to form a wide range of intercalation compounds in
which C60 act as an electron acceptor