Atomic and Ionic Arrangement

Essentials of Materials Science and Engineering D. R. Askelard & P. P. Fulay

Solid State Chemistry – An Introduction Smart & Moore
 Bravais Lattice and Crystal system

The structures of crystals can be classified according to the symmetry of the

unit cells. There are in total 7 groups (in 3D space), collectively called crystal
systems. Each crystal system is governed by the minimum presence/absence
of symmetry in the structure.

A lattice is a periodic array of points, on which a crystal is built. Identical

points can be arranged spatially to produce 14 types of regular pattern 3D
spaces, respectively. These space lattices are known as 'Bravais lattices'.
Crystal system & Bravais Lattices

Unique arrangement of unit cell Arrangement of lattices

(crystal system) Bravais Lattices
i) Triclinic P
ii) Monocinic P, S (C or A)
iii) Orthorhombic P, C (A or B), I, F
iv) Tetragonal P, I
v) Hexagonal P
vi) Rhombohedral R
vii) Cubic P, I, F

P C I F R refer to the different lattice cenering

 Crystal system and Bravais Lattices
Crystal system Essential Bravais Axes Angles between
Symmetry Lattices axes

Cubic Four 3-fold P, I, F a=b=c α=β=γ=90°

axes
Tetragonal One 4-fold P, I α=β=γ=90°
axis
Orthorhombic Three 2-fold P, C, I, F α=β=γ=90°
axes

Hexagonal One 6-fold P α=β=90°, γ=120°

axis
Rhombohedral One 3-fold R a=b=c =β≠
axis

Monoclinic One 2-fold P, C α=γ=90°, β≠90°

axis prep. to b
axis
Triclinic - P
 Crystal system and Bravais Lattices

P = primitive (there is only one reticular point inside the cell

C = centered in the faces perpendicular to the cell c axis (+ 1/8
of reticular point in each corner)
I (Innenzentriert) = centered in the body of the cell (+ 1/8 of
reticular point in each corner)
F = centered in all faces of the cell (+ 1/8 of reticular point in
each corner)
R = primitive, identical cell axes and cell angles (+ 1/8 of
reticular point in each corner)

Q
If we have A-, B, C-, I- F- centred cells, and there are 7 primitive
Bravais lattices, why are’n there are 5x7=35 non-primitive lattices?

standard notation for this Bravais lattice type is given

 Why certain Bravais Lattices are not tabulated?

Crystal system Bravais Lattices

i) Triclinic P
Show that following Bravais lattices are equal ii) Monocinic P, C
(a) C-tetragonal and P-tetragonal iii) Orthorhombic P, C (A or B), I, F
(b) F-tetragonal and I-tetragonal iv) Tetragonal P, I
(c) B-monoclinic and P-monoclinic (b-unique axis) v) Hexagonal P
(d) C-monoclinic and I-monoclinic (b-unique axis) vi) Rhombohedral R
vii) Cubic P, I, F

Arrangement of lattices absent:

(a) Violate symmetry requirement
(b) Represented by smaller alternative cell
(tetragonal F tetragonal I)
Crystal structure of elements in the periodic table
 Crystal structure characteristics of some metals

Elements Structure atom/cell a vs r Coordination Packing Volume

number factor

α-Po Simple cube (sc) 1 a=2r 6 0.52 a3

Fe, W, Mo, Nb, Body-centred cube 2 8 0.68 a3

Ta, K, Na , V, Cr (bcc)
Cu, Au, Pt, Ag, Face-centred cube 4 12 0.74 a3
Pd, Ni (fcc)
Ti, Mg, Zn, Be, Hexagonal close- 6 a=2r 12 0.74 2.598a2c
Co, Zr, Cd packed (hcp) c/a=1.633

The majority of the elements crystallize in ccp(fcc), hcp, or bcc lattices

α-Polonium adopts a simple cubic structure
 Number of atoms per unit cell
Face cantered atom is shared
between two unit cells

Each corner atom shared by eight unit cells

1-4 in the front and 4-8 in the back
Number of atoms per cubic unit cell
How many atoms in the unit cell of the following?

Lattice point per cell =1

Basic or motif =1
(Each lattice point has
only one atom)
 Atomic radius (r) and lattice parameter (a)
Basic or motif =1
(Each lattice point has only one atom) cubic unit cell
Atoms are hard sphere
Atoms touch their close neighbours

2r=a 4r=√3a 4r=√2a

 Coordination Number
Number of nearest neighbours for a particular atom
SC unit cell

Basic or motif =1
(Each lattice point has only one atom)

CN=6
Coordination Number
bcc unit cell

Basic or motif =1
(Each lattice point has only one atom)

CN=8
Packing factor (PF)
 Packing factor for SC unit cell

Basic or motif =1
(Each lattice point has only one atom)
Atoms are hard sphere
Atoms touch their close neighbours SC
Packing factor for fcc unit cell
Packing factor for bcc unit cell

2
 hcp unit cell
Hexagonal prism

Each corner atom is shared by 6 unit cells

Basic or motif =2
Each face cantered atom is shared by 2 unit cell.
(Each lattice point has 2 atoms)
Atoms are hard sphere 3 atoms in the form of triangle midway between two
Atoms touch their close neighbours
basal planes

touch
Volume of hcp unit cell
 hcp unit cell
In metals with ideal hcp structure, c/a =√8/3=1.633

Baudhayana Sutras (Sulba Sutras)

C X

a c/2 A
x
X
A

Most, hcp structures c/a ratio differ slightly from ideal vaules.
 Packing factor for hcp unit cell

For hcp unit cell,

a=2r
V=2.598a2c
c/a=1.633
hcp unit cell
(hP)

A primitive hexagona structure

The unit cell is a skewed prism
Number of lattice point =1
basic=2 (2 atoms are associated with each lattice point)
Number of atoms in an unit cell=6/3=2
Volume of the unit cell=2.598a2c/3=0.866a2c.
Q. Calculate the density of bcc Fe which has a lattice parametre 0.2866 nm Atomic mass of Fe=55.487
g/mol.
 Points, Directions, and Planes in the Unit Cell

Essentials of Materials Science and Engineering D. R. Askelard & P. P. Fulay

 Points and Fractional Coordinate
Right hand coordinate system Coordinate: Written in term of lattice parameter

Fractional coordinate: (x/a, y/b, z/c)

Example
a=1000 pm atom at 500 pm
(0/a, 0.5b/b, c/c)
fractional coordinate=x/a=0.5.

1,0,0
(0.5a/a, a/a, 0/a)

(a/a, 0/b, 0/c)

Three distances with commas separating the numbers
 Direction in the Unit Cell

Miller indices are used to identify the directions in the following procedure

i. Using a right-handed coordinate system, determine the coordinates of two

points that lie on the direction.
ii. Subtract the coordinate of the tail points from the coordinates of the head
points.
[Link] the fraction and/or reduce the results obtained from the subtraction
to lower integers.
iv. Enclose the resulting numbers in the square bracket []. Negative number
should be written with a bar over the number .
 Directions in the Unit Cell
Direction A
1. The two points are 0,0,0 and 1,0,0.
2. 1,0,0-0,0,0=1,0,0
3. No fraction to clear or the integer to reduce
4. [100]
Direction B
1. The two points are 0,0,0 and 1,1, 1.
2. 1,1,1-0,0,0=1,1,1.
3. No fraction to clear or integers to reduce.
4. [111].

identical
• Certain groups of directions are equivalent. The group of equivalent directions are referred as directions of a form (<>).
Directiona of the form <110> in cubic systems

0,0,0

1,1,0

A material has the same properties in each of these 12 directions of the form <110>.
 Lattice plane
Lattice planes, that are a concept introduced with Bragg’s Law (nλ=2dsinθ), are defined purely from the shape and
dimensions of the unit cell. Lattice plane are entirely imaginary and simply provide a reference grid to which the atoms in
the crystal structure may be referred.
A plane is indexed hkl when it makes the intercepts a/h, b/k, c/l, with the unit
cell edges a, b, c, respectively.

d’

O
0,0,0

Lattice planes are labelled by assigning three numbers known as Miller indices to each set.

A plane and all other planes that are parallel to it and separated from adjacent planes by the same d-spacing give
same Miller indices.
 Planes in the Unit Cell

Miller indices are used to identify the plane in the following procedure

i. Identify the points at which the intercept the x, y, z in term of lattice

parameters. If the plane passes through the origin, origin of the coordinate
system must be moved.
ii. Take the reciprocals of the intercepts.
[Link] the fraction but do not reduce to the lower integers.
iv. Enclose the resulting numbers in parenthesis (). Negative number should
be written with a bar over the number .
Determine the Miller Indices of Planes
 12

In each unit cell, planes of a form represents groups of equivalent planes due to their orientation of the coordinate.
The planes of a form {110}in cubic systems are (110), (101), (011), (11 0), (1 0 1), (01 1).
 Planer Density, Packing Fraction

Q-2 Calculate the planer density and planer packing fraction for the (010) and (020) planes in α-Po which has a lattice
parametre of 0.334 nm.
Hint. Planer density= atom per face/area of a face and Packing fraction = area of the atoms per face/ area of the face

Answer. Planer density (010) =8.89 atoms/nm2 and Packing fraction (010) =0.79
Planer density (020) =0 and Packing fraction (020)=0
(010) and (020) planes are not equivalent.
Miller Indices for Hexagonal Unit Cell
Miller-Bravais indices for Hexagonal unit cell
plane
4-axis system a1, a2, a3, c
a3 axis redundant
(0001)
(hkil)

-i=(h+k)

A=(0 0 0 1)
B=(1121)
C= [101] or [2113]
D= [110 ] or [1100 ]
Direction
3 (h´, k´, l´) or 4-axis system (hkil)
-i=(h+k).