Solids
(reading assignment on micelle
formation and membrane formation)
Lattices and unit cells
Structural motifs
Space lattice: pattern formed by points
Properties of space lattice:
(i) An imaginary scaffolding
(ii) 3D infinite array of points
Unit cell: an imaginary parallelipiped
Properties of a unit cell:
(i) Fundamental region –bricks on a wall
(ii) Primitive unit cell
*An inifinite number of unit cells can describe the same
lattice but the one with sides that have the shortest
lengths and that are the most nearly perpendicular to
one another is normally chosen
Parameters defining the unit cell:
(i) Length of the sides- a,b,c
(ii) Angles between the sides - , ,
B rava i s L att i c e s
Seven crystal systems are each described by the shape of the unit cell which can be
translated to fill space.
Bravais lattice – 14 simple and complex lattices within the seven crystal system
Identification of lattice planes
Spacing between lattice planes is a quantitative property of the
crystal lattice
There are different sets of planes in the lattice
Analysis strategy:
(i) Consider a 2-D rectangular lattice formed from a unit cell of
sides a and b
(ii) Each plane can be distinguised by the distance at which it
intersects the a and b axes
(1a, 1b) (1/2a, 1/3b) (-1a, 1b) (a, 1b)
(iii) Intersection distances along the axes are quoted as multiples of
the lengths of the unit cell
(1, 1) (1/2, 1/3) (-1, 1) (, 1)
(iv) We add the 3rd dimension – the unit cell has a length c in the z-
direction planes intersect the z-axis at
(1, 1, ) (1/2, 1/3, ) (-1, 1, ) (, 1, )
(v) Presence of fractions and infinity is inconvenient . We take the
reciprocals of intersection distance
(h k l) – Miller indices
Miller indices of the four sets of planes:
(a) (1 1 0) (b) (2 3 0) (c) (1 1 0) (d) (0 1 0)
Example: 3D representation of planes
Observation:
(i) The smallest the absolute value of h (or k or l) in (hkl), the more nearly
parallel the plane is to the a-axis (b-or c-axis)
(ii) When h (k or l) equals 0, the plane is parallel to the a-axis (b- or c-axis)
(iii) The notation (hkl) denotes an individual plane
(iv) The notation {hkl} denotes the set of planes parallel to the plane (hkl)
The separation of planes
Separation of the {hkl} planes in the square 2D lattice
h2 k 2 a
1
or d hk 0
2
d hk 0 a2 h2 k 2
Separation of the {hkl} planes in a cubic lattice
h2 k 2 l 2 a
1
or
d hkl
2
d hkl a2 h2 k 2 l 2
Expression for a general orthorhombic lattice
1 h2 k 2 l 2
2
2 2 2
d hkl a b c
Investigation of structure
Waves interfere with one another
Greatest displacement where peaks or troughs coincide
Smaller displacement where peaks coincide with troughs
Intensity of electromagnetic radiation is proportional to the
amplitude of the wave
regions of constructive/destructive interference have
enhanced/diminished intensities
Diffraction: interference caused by an object in the path of waves
Diffraction pattern: pattern of varying intensity resulting from diffraction
Diffraction occurs when the dimensions of the diffracting object are
comparable to the wavelength of the radiation
X-ray Diffraction
X-rays have wavelength ( Å) comparable to the separation of lattice planes
X-rays can be used in the determination of structures
XRD is almost fully automated: banks of structural data
X-ray generation:
(i) Bombardment of a metal with electrons of high KE
1
EK me v 2
2
(ii) Deceleration of electrons (interaction of incoming
electrons with the metal electrons and the nuclei
change of direction and loss of kinetic energy)
generation of radiation with continuous range of
wavelengths (Bremsstrahlung)
High-intensity, sharp peaks are superimposed on the deceleration radiation
(iii) Incoming electrons expel inner-shell electrons
vacancy (hole) generation
vacancy is filled by an electron dropping from a higher energy level
emission of characteristic radiation (sharp peaks; n=1 K, K ...... Lines
n=2 L ,L
Von Laue‘s approach: passing a broad-band beam of X-rays into a single
crystal and recording photographically the diffraction patterns
Debye-Scherrer method:
(i) Uses monochromatic radiation and a powder sample
(ii) Some crystallites are oriented so as to give rise to diffraction
(iii) intensities of reflections are monitored as the detector rotates around the
sample
Application:
(i) Identification of a solid substance by
comparison of the diffraction lines and their
intensities with a data bank (diffraction patterns)
(ii) Determination of phase diagrams
(iii) Determination of relative amounts of each
phase in the substance
Bragg‘s Law (used a single crystal and a monochromatic x-ray and rotate the
crystal until a reflection was detected)
Lattice plane is treated as a mirror
Crystal lattice is regarded as a stack of reflecting lattice planes of separation d
Model facilitates the calculation of the angle the crystal makes to the incoming
beam of X-rays for constructive interference (X-ray reflection)
Analysis strategy: reflection of two parallel rays
of the same wavelength () by two adjacent
planes
- glancing angle
Extra distance (path length) traveled by one ray
AB+BC= 2d sin (net path length)
Constructive interference (extra path
length=integral number of wavelengths
Bragg‘s Law n= 2d sin
Reflections with n= 2,3,.... are called second-order, third-order, etc.
Application of Bragg‘s Law: determination of the spacing between the layers in the
lattice
