Band Theory

This is a quantum-mechanical treatment of bonding in metals. The spacing between energy levels is so minute in metals that the levels essentially merge into a band. When the band is occupied by valence electrons, it is called a valence band. A partially filled or low lying empty band of energy levels, which is required for electrical conductivity, is a conduction band. Band theory provides a good explanation of metallic luster and metallic colors.

Antibonding

bonding

The 2s Band in Lithium Metal

Anti-bonding

Conduction band
ee-

Valence band
Bonding

Band Overlap in Magnesium

Conduction band

Valence band

Band Structure of Insulators and Semiconductors

Density of state = dn/dE

n = number of states

(a)

(b)

Density of states in (a) metal, (b) semimetal (e.g. graphite).

Conductivity of Graphite
insulator

e- -conductor

Fermi level- the highest occupied orbital at T= 0

(a)

(b)

Fermi distribution (a) at T= 0, and (b) at T> 0. The population decays exponentially at energies well above the Fermi level. 1 Population, P = ( E ) / kT where, = chemical potential +1 e When E= , P= 1/2

(a)

population

(b)

Fermi distribution at T> 0 for (a) Intrinsic semiconductor, (b) Fermi distribution and the band gap

Extrinsic semiconductor: (a) n-type, e.g. P doped Si (b) p-type, e.g. Ga doped Si.

Structural Defects
Intrinsic defects- occur in the pure substance Extrinsic defects- stem from the presence of impurity Point defects Extended defects- in one, two or three dimension

Intrinsic Point Defects

Shottky defectMissing ion-pair

Frenkel defectmisplacing ions to interstitial

Atom exchange defect

Extrinsic Point Defects

F-center defect

Defect sites of FeO

Fe2+ Oh sites

Nonstoichiometry of FeOx One Fe(II) vacancy is chargecompensated by 2 Fe(II) 2 Fe(III)

Stoichiometry FeO

FeOx

Phase diagram of Iron Oxides as a Function of Oxygen Content

Plane Defects

Shear plane: formation upon Oxygen- removal

Shear plane High resolution SEM on (120) in WO 3-x

Ion Conductivity
Diffuse mechanisms for ions or atoms in a solid:
(a) exchange (b) interstitialcy (c ) interstitial (d) vacancy

Ag2HgI4

(a) low-temperature order structure (b) high-temperature disordered structure a Ag+-conductor

-Alumina

a Na+-conductor

Activation Energy of Ion-Conductor

Arrhenius plot of the logarithm of the diffusion coefficient of the mobile ion k = A exp(-Ea/RT)

an O2--conductor

Eg

Overlapping of d-Orbitals of Early Transition Metal Elements in the Oxide Structures

Energy Level Diagram of Early Transition Metal Elements in the Oxide Structures

Magnetic Properties of Materials with Long-Range Ordered Spins

Ferromagnetic

Antiferromagnetic

Molar magnetic susceptibility,

In a magnetic field, H, the magnetic induction, B, in the material is B = H + 4I, where I= magnetic moment/ volume magnetic permeability, P = B/H = 1 + 4 I/H = 1 + 4 magnetic susceptibility, = I/H = F/d, where F= formula weight d= density of the material Curie-Weiss Law: = C/(T + ), C: Curie constant; : Weiss constant

Curie temperature

Neel temperature

Intercalation Reactions
C(graphite) + n K(s) CKn (Cn-, n K+) C(graphite) + n/2 Br2(g) CBrn (Cn+, n Br-)

Hosts for Intercalation

Intercalation Reaction in Lithium Battery

High temperature superconductor

YBa2Cu3O7

Synthesis of Solid (Oxide) Materials by Sol-Gel Method

Diffraction Pattern

<Ref> Structure determination by X-ray crystallography M.F.C. Ladd and R.A. Palmer, NY : Plenum Press, 1985.

14 Bravais Lattice

Miller Indices (hkl): a plane in the crystal lattice

h = a/cutting point along a-axis k = b/cutting point along b-axis l = c/ cutting point along c-axis

Miller Indices (hkl)

Face cutting 1a and 1b Face cutting 1b and 1c Face cutting -1/2a, 1/2b and 1/2c

Crystallographic data

2dsin = n sin = n/2 (1/d)

Reciprocal lattice

Reciprocal lattice

Stereographic projection

Conventional graphic symbols

Special points in the Cubic System (O or 432) falling on rotational axes along with the Miller indices of the projection plane

Stereogram of the C4v group, with a general point E and the locations to which it is moved by the symmetry operations indicated.

Space Group- containing space symmetry operations

1) Screw Axes

31 screw axismoving 1/3 distance along one unit cell dimension, then rotating for 2/3

2) Glide Planes

a glidemoving 1/2 distance along a-axis, then reflecting versus ac-plane (or ab-plane)

a, b, c glidemoving 1/2 distance along a, b or c-axis, then reflecting n glidemoving 1/2 distance along face-diagonal, then reflecting d glidemoving 1/4 distance along body-diagonal, then reflecting

Space Group P 21
primitive

Screw axis 21

Screw axis

3 1 4

1 at 0, 0, 0 (the origin) 21 parallel to the Y-axis, distance from ab-plane c (010), normal to the Y-axis 21 c x, y,z (1) -x, +y, -z (2) -x, -y, -z (3)