c
 




c  

M


@ A lattice is an infinite array of points where each point has identical surroundings

@ A unit cell is a building block, which when repeated in all directions, gives the lattice

@ A lattice point specifies the location of a structural motif

@ A crystal lattice is the array of lattice points

@ A crystal structure is the collection of structural motifs arranged according to the

lattice

Unit Cells

@ The position of a unit cell is not unique

@ 4 types of unit cells:

@ Primitive (P) ± 1 lattice point (8 x 1/8)

@ Body-centred (I) ± 2 lattice points (1 + 8 x 1/8)

@ Face-centred (F) ± 4 lattice points (1/2 x 6 + 1/8 x 8)

@ C-centred ± 2 lattice points (1/2 x 2 + 1/8 x 8)

@ Any unit cell can be defined by a parallelpiped with 6 parameters a, b, c and ,
, 

@ There are only 7 possible unit cell shapes, which when combined with the 4 possible
lattices, give 14 Bravais lattices (CTORHMT)

Miller Indices

@ Refer to the reciprocals of intersection distances used to denote planes in crystals

@ Has the form (hkl) corresponding to the no of divisions on the a, b and c axes
respectively

@ The separation between planes is represented by d hkl

Crystal Structure Determination

@ To generate the X -ray radiation, high energy electrons are fired at metal samples like
Cu. The electrons excite core electrons, leaving a vacancy. The excited electron
drops back into the vacancy, emitting X -ray radiation. The emitted quantised
radiation is usually filtered to produce monochromatic X -rays.
Bragg¶s Law

For constructive interference, AB+BC must be an integer multiple of ½

n½ = AB + BC

AB = BC = d sin

Path difference = Œ
 ½

Note: ½ is the wavelength of the incident monochromatic radiation (usually 1.542 Angstrom)

½
  



@ For atoms or molecules with isotropic interactions, optimal packing results in minimal
volume and maximal density

@ A single layer of spheres is closest-packed with a hexagonal coordination of each

sphere

@ A second layer of spheres is placed over the top of µholes¶ of the first layer
(generating octahedral holes with 6 nearest sphere neighbours and tetrahedral holes
 with 4 nearest spher e neighbours)

@ When the third layer is placed, 2 choices:

@ The third layer lies eclipsed with the first layer (directly in line) ABABAB (HCP)

@ OR It lies in the alternative holes leaving it staggered with respect to both layers
ABCABC (CCP)

@ Since the difference between the 2 structures arises in the 3 rd coordination shell,
HCP vs CCP is usually very finely energetically balanced

@ CCP/HCP have 74% packing efficiency compared to BCC of 64% (less favourable)

@ CN=12 for close-packed structures (6 in the sa me layer, 3 above and 3 below)

@ Note: HCP has 6 atoms per unit cell (3 + ½ x 2 + 12 x 1/6) while CCP has 4 atoms
per unit cell (8 x 1/8 + 6 x ½)

@ Polymorphism refers to the ability of a mate rial to adopt different packing

arrangements (CCP  HCP  BCC)

@ CN remains the same, very small energy difference between structures

@ Polytypism refers to the variation in stacking sequences within a structure

@ E.g. ABAB’
ABAB


 

  

  
 


 


MM½
6:6 (octahedral;
CCP Cl- with Na+ in
NaCl FCC topologically
all O holes
identical)
Ca2+ is 8
CCP Ca2+ lattice
coordinated (cubic)
CaF2 with F- in all T holes. FCC
F- is 4 coordinated
4 CaF2 per unit cell
(tetrahedral)
CCP S2- lattice with
4:4 (tetrahedral;
Zn2+ in half the T
ZnS (zinc blende) FCC topologically
holes.
identical)
4 ZnS per unit cell


MM½
HCP array of S2-
with Zn2+ in half the
ZnS (Wurtzite) Hexagonal Primitive 4:4 (tetrahedral)
T holes
2 ZnS per unit cell
HCP As with Ni in all Ni: 6 (octahedral)
NiAs O holes Hexagonal Primitive As: 6 (trigonal
2 NiAs per unit cell prismatic)
HCP I with Cd in O
Cd: 6 (octahedral)
CdI2 holes of alternate Hexagonal Primitive
I: 3 (base pyramid)
layers
TiO2 (rutile)
(compare with CdI2 ±
half of O holes in Distorted HCP O
Ti: 6 (octahedral)
TiO2 are full but all lattice with Ti in half
O: 3 (trigonal planar)
holes are full in the O holes
alternate layers of
CdI2)

½M

1 CsCl per unit cell
8:8 (large cations, so
Can be regarded as
CsCl Cubic Primitive more anions can be
2 interpenetrating
packed around )
primitive cubic cells
  

8 coordination Cuboidal CsCl structure

0.732

6-coordination Octahedral NaCl structure

0.414

4 coordination Tetrahedral ZnS structure

0.225

 
   

@ LE is the energy change when 1 mole of gaseous ions, which are infinitely separated,
form a crystal at 0K

@ Always exothermic so H < 0

@ Long range attractive forces between unlike charges

@ Short range repulsion at close range between electrons of one ion and that of
neighbouring ions

Coulomb attraction
   
ù


 

@ Where U = change in internal energy (in J)

ZA = charge on ion A
ZB = charge on ion B
r = internuclear distance between ions (in m)
0 = permittivity of a vacuum (8.854 x 10 -12 Fm-1)
e = charge on an electron (1.602 x 10 -19 Cm-1)
 @ Individual interactions will be negative (attractive) between unlike charges and
positive (repulsive) between like charges

@ Need to sum up all the pairwise interactions

Madelung constants
    
ù


 

@ Where NA = Avogadro¶s no and A = Madelung constant (structure specific)

@ E.g. for NaCl, sit on central Na+ and consider neighbour distances

6 Cl - (face of cube) at distance r

12 Na + at distance m 
8 Cl - (corner of cube) at distance m


@ Sum up all interactions and it can be shown that the sum converges to a constant
value

@ A = sum of [charge x 1/distance relative to r]

= (6 x 1/1) ± (12 x 1/m ) + (8 x 1/m
) ± (6 x ½) + ...

Repulsive Component

ù



@ Where n = Born exponent (obtaine d from experimental compressibility data) and

B = repulsive constant

Overall,

     
ù
  

  


Find
 and rearrange to find B and substitute B into original expression for U


Born Lande equation

    

   

 

Hess¶ Law

@ The enthalpy change for a reaction is independent of the pathway it takes provided
the initial and final states of the reaction remain the same
Kapustinskii equation

    

ù
   "#$%& '(
! !

@ Where d = distance between cation and anion (r+ + r -), assuming touching spheres
(in Angstrom)

@ Compare ionisation energy with lattice enthalpy to predict which compound formed is
more favourable