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24 views26 pages

Arc L2

Uploaded by

angshurc
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chemical Crystallography

Dr. Angshuman Roy Choudhury


Unit Cells and Crystal Systems

ISSUES TO ADDRESS...
• Concepts about unit cell, crystal lattice and
crystal systems
• Crystallographic symmetry elements, point
groups and space groups.

• Crystallographic directions, planes and their


significance.

1
What is Crystal ?
A crystalline material is one in which atoms or ions are
situated in a repeating array over large atomic
distances.
Atomic Hard Sphere model
“Lattice” Three dimensional array of points
coinciding with atom positions
Crystal = Lattice (arrangement of atoms) +
Motif (associated atoms or group of atoms)
“Unit Cell” smallest repeat unit in crystal structure,
contains the symmetry information. Unit cells are the most
elementary arrangement of atoms which can generate the
entire crystal upon application of suitable translation,
rotation, mirror, or inversion operations.
Crystal Systems
Crystals are grouped in terms of 6 parameters :
a, b, c,  , 
7 Crystal Systems & 14 Bravais Lattices
Volumes of Different Crystal structures

Cubic = a3
Tetragonal = a2c
Orthorhombic = abc

Hexagonal = 0.866 a2c


Trigonal = a3 (1-3 cos2 + 2 cos3)1/2
Monoclinic = abc sin
Triclinic = abc (1- cos2 - cos2 - cos2 + 2 cos  cos  cos  )1/2
Unit cell arrangement of simple cubic system

Coordination number = 6
Contribution to unit lattice = 1/8
Unit cell arrangement of BCC system

Coordination number of corner


atom = 8

Contribution to unit lattice = 1/8


(Corner), 1 (Centre).
Unit cell arrangement of FCC system
Coordination number = 12
Contribution to unit lattice = 1/8
(Corner), ½ (Faces).
Q. Why C centred Monoclinic unit cell is equivalent to body centred
Monoclinic unit cell?

Q. Why face cantered tetragonal system does not exist?


Symmetry Elements, point groups
and
Space Groups
THEORETICAL DENSITY, r
#atoms/unit cell Atomic weight (g/mol)

  nA
Volume/unit cell Vc NA Avogadro's number
(cm3/unit cell) (6.023x 1023 atoms/mol)

Data from Table inside front cover of Callister:


• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10-9 m)
Vc = a3 ; For FCC, a = 4R/ -23cm3
 2 ;Vc = 4.75 x 10
3
Result: theoreticalCu = 8.89 g/cm

Difference between theoretical and measured density is a consequence of defects


Crystallographic Points, directions and Planes

Right handed coordinate system of three (x, y, z), situated at a corner of


the cell and coinciding with the edges.

Point Coordinate: It is specified in terms of its coordinates as fractional


multiple of unit cell length. They are not separated by comma.
Find out point coordinates for all atom positions for a
BCC unit cell.
(001) (011)

(101) (111)

(½½½)

(000) (010)

(100) (110)

Find out point coordinates for face atoms positions for a


FCC unit cell.
Crystallographic directions: Miller indices
1. Use right handed coordinate system and find out the coordinates of two
point that lie on the direction.
2. Subtract the coordinates of the ‘tail’ point from the coordinates of the
‘head’ point to obtain the number of lattice parameters travelled in the
direction of each axis of the coordinate system.
3. Clear fractions and reduce to lowest integers.
4. Enclose the numbers in square brackets [ ]. If a –ve sign is produced,
replace the –ve sign with a bar over the number: Miller indices for
directions
For a cubic unit cell, the symmetry of the geometry means that many
equivalent directions can be combined into a family. The spacing of atoms in
equivalent direction is the same.
Edge directions; <100> : [100], [010], [001], [100] [010] and [001]
Face diagonals; <110>
Body diagonals ; <111>
Directions with same indices, without regard to order or sign: [123]
[231] [12 3] ……
Important facts:
• Directions are vectors: A direction and its –ve are opposite directions.
• Directions and its multiple are identical: [100] is same as [200]
What is the relation between [111] and [111]? Anti-parallel direction

Determine the miller indices of the directions between the following points.
1. (½,1,0)  (0,0,1). [122]
2. (0,0,0)  (1,1,1). [111]
3. (1,0,0)  (0,1,0). [110]
4. (1,½,1)  (½½½). [101]
5. (1,1,1)  (0,½,0). [212]
Crystallographic Planes
1. Identify the points at which the plane intercepts the x, y, z coordinates
in terms of lattice parameters. If the plane is passing through the
origin, origin of the unit cell must be moved.
2. Take reciprocals of these intercepts.
3. Clear fractions but do not reduce to lowest integers.
4. Enclose the resulting numbers in parenthesis ( ). Negative numbers
should be written with a bar over the number.

A  Intercepts are x = 1, y = 1, z = 1
 Reciprocals: 1, 1, 1. So the plane is (111)
B  Intercepts are x = 1, y = 2, z = .
Reciprocals: 1, ½, 0.
Clear fraction: 2 1 0, So the plane is (210)

C  This plane passes through (000).


Move origin to one lattice parameter in +y
direction: Intercepts  x = , y = -1, z = .
 Reciprocals: 0, -1, 0.
The plane is (010).
(100) (110)

(111) (210)
Some General Principles

If a Miller index is zero, the plane is parallel to that axis.

The smaller a Miller index, the more nearly parallel the plane
is to the axis.

The larger a Miller index, the more nearly perpendicular a


plane is to that axis.

Multiplying or dividing a Miller index by a constant has no


effect on the orientation of the plane

Miller indices are almost always small.


Draw the following planes in the unit cell:
(100), (200), (121), (121), (111)
Important aspects of the Miller indices for planes:

1. Planes and their negatives are identical (this was not the case for
directions)
2. Planes and their multiples are not identical (opposite for direction). It
means (100) and (200) are not same.
3. In each unit cell, planes of a form represent groups of equivalent
planes that have their particular indices because of the orientation of
the coordinates. This groups of similar planes are represented with
the notation  .
4. In cubic systems, a direction that has the same indices as a plane is
perpendicular to that plane.

Due to the symmetry of crystal structures the spacing and arrangement


of atoms may be the same in several planes. These are known as
equivalent planes, and a group of equivalent planes are known as a
family of planes.
Equivalent planes
Repeat Distance and Linear density
Repeat distance = The distance between two adjacent lattice points in an unit
cell.

• For simple cubic: Repeat distance is same as edge length = a 0.

• For FCC lattice: Repeat distance is ½ of face diagonal = ½√2a0


• For BCC lattice: Repeat distance is ½ of body diagonal = ½√3a0
Linear density = The number of lattice point per unit length along a
crystallographic direction.

Linear density = (number of repeat distances)/(length of the direction vector


in the unit cell)
Say for FCC Cu, a0 = 0.36151 nm.
Repeat distance is ½ of face diagonal = ½ √2a0 = 0.256 nm
Linear density = (2 repeat distances)/√2a0 = 3.91 lattice points/nm
Linear density is the reciprocal of the repeat distance
Planar density = (number of atoms centred on a plane)/(area of the plane)

(110) Plane of FCC


Number of atoms = 2; area = 4R x 2R 2
PD110 = 2atoms/8R22

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