Lecture 03

Introduction-1
Three dimensional Point Groups

Symmetry elements
Rotation axes: 1,2,3,4 and 6 fold rotations
Reflection plane: Reflection in a plane through a lattice point denoted by m
Inversion centre: denoted by 1
Rotation-inversion: Rotation followed by inversion
3
4
Denoted by: 1, 2, = m, 3, 4, 6
Number of point groups: 32

Number of Bravais lattice: 14
Number of space groups: 230
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In 2D centering was very simple, since a parallelogram has only one face. In 3D we
have more options, leading to six different centering arrangements.
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Centering
Symbol
Centering Vector(s)
Lattice Points per

Unit Cell
Face Centered
a + b
a + c
b + c
Body Centered
a + b + c
Base Centered
a + b
a + c
b + c
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Introduction-2

Note that there are three different ways to center in only one set of
opposing faces of the unit cell (base centered), depending upon whether
the opposing faces lie in the ab plane (C-centered), the ac plane (Bcentered) or the bc plane (A-centered).
Combining the crystal systems (primitive translational symmetry) and
the centering translations, produces 14 unique Bravais Lattices
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In 3D there are 7 crystal systems:
Triclinic
Monoclinic
Orthorhombic
Trigonal (Rhombohedral)
Hexagonal
Tetragonal
Cubic
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Introduction-3

The 32 Crystallographical point groups
Crystal System
Number of Point
Groups
Herman-Mauguin Point
Group*
Schoenflies Point
Group
Triclinic
1, 1
C1, Ci
Monoclinic
2, m, 2/m
C2, Cs, C2h
Orthorhombic
222, mm2, mmm
D2, C2v, D2h
Trigonal
3, 3, 32, 3m, 3m
C3, S6, D3, C3v, D3d
Hexagonal
6, 6, 6/m, 622,
6mm, 6m2, 6/mmm
C6, C3h, C6h, D6, C6v,

D3h, D6h
Tetragonal
4, 4, 4/m, 422,
4mm, 42m, 4/mmm
C4, S4, C4h, D4,

C4v, D2d, D4h
Cubic
23, m3, 432, 43m

m3m
T, Th, O,
Td, Oh
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International point group notation
Rotation axis
Rotation inversion axis
4/m
Rotation axis with mirror plane normal to it
32
Rotation axis with diad axis(axes) normal to it
4mm
Rotation with mirror plane parallel to it
4 2m
Rotation-inversion axis with diad axis normal
4/mmm Rotation axis with mirror planes normal and parallel to it
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Introduction-4
Stereogram
Stereogram of cube having point group m3m
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Stereogram
Symmetry elements of a cube (reflection planes)
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Introduction-5
Stereogram
Symmetry elements of a cube (rotations)
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Stereogram
Symmetry elements of a cube (All)
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Introduction-6
3 dimensional Bravais Lattice

Crystal System
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The 14 Bravais Lattices

Fourteen Bravais lattices
Cubic I
Cubic P
Monoclinic
Cubic F
Rhombohedral (trigonal) R
Tetragonal P Tetragonal I
Hexagonal P
Orthorhombic
Triclinic P
P
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Introduction-7
Three dimensional Space Groups

Enumeration of simple space groups (Symmorphic)
Crystal System
Number of Point
Groups
Number of Bravais
Lattices
Product
Triclinic
Monoclinic
Orthorhombic
12
Trigonal
Hexagonal
Tetragonal
14
Cubic
15
Total
32
14
61
Placing trigonal point group in hexagonal Bravais lattice: 5 more space groups- Total =66
Object with symmetry of given point group oriented in more than 1 way in Bravais lattice results in
more space groups Total =73
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Non-Symmorphic space groups
Glide planes and screw axis
Glide plane combines a reflection plane with translation parallel to the
plane
In 2D there is no ambiguity in the direction which is parallel to the
mirror plane.
However, in 3D we have several choices of translation vectors parallel to
the glide plane.
This leads to a greater variety of glide planes, each of which has a unique
symbol.
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Introduction-8
Rotation and inversion
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Screw rotations
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Introduction-9
Glide plane (Glide reflection)

The various glide planes in 3d, their symbols and the displacement vector associated with each
are given in the table below.
Herman-Mauguin Symbol
Axis
to the Glide Plane
Displacement Vector
b or c
a/2
a or c
b/2
a or b
c/2
n*
a
b
c
b/2+c/2
a/2+c/2
a/2+b/2
d**
a
b
c
b/4+c/4
a/4+c/4
a/4+b/4
*In
rare cases the diagonal glide (n-glide) can also have a displacement vector of a/2+b/2+c/2.
glides (d-glide) can only occur in F and I centered lattices. As in the diagonal glide
they may also take the form a/4+b/4+c/4 in rare cases.
**Diamond
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Glide planes
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Introduction-10
Glide plane (Glide reflection)

The various glide planes, their symbols and the displacement vector associated with each are
given in the table below.
Herman-Mauguin Symbol
Axis
to the Glide Plane
Displacement Vector
b or c
a/2
a or c
b/2
a or b
c/2
n*
a
b
c
b/2+c/2
a/2+c/2
a/2+b/2
d**
a
b
c
b/4+c/4
a/4+c/4
a/4+b/4
*In
rare cases the diagonal glide (n-glide) can also have a displacement vector of a/2+b/2+c/2.
glides (d-glide) can only occur in F and I centered lattices. As in the diagonal glide
they may also take the form a/4+b/4+c/4 in rare cases.
**Diamond
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Screw rotation
A NM screw rotation operation consists of a 360/N rotation followed by a
displacement of M/N the unit cell dimension parallel to the axis.
For example a 31 screw axis parallel to the c-axis represents a 120
rotation followed by a displacement of 1/3c.
(a) Mirror reflection

(b) Glide reflection
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(a) Rotation diad axis 2

(b) Screw diad axis 21
20
(a) Rotation triad axis 3

(b) Screw triad axis 31
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Introduction-11

Symmorphic space groups: total =73
Additional operations of glide planes and screw axes
This requires a special relation between the dimensions of the basis and
the dimensions of the Bravais lattice
Space groups containing these operations are non-symmorphic
When these operations are included total space groups = 230
For detailed tutorial on space groups visit
img.chem.ucl.ac.uk/sgp/MAINMENU.HTM
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Summary
A space group is a representation of the ways that the
macroscopic and microscopic symmetry elements (operations)
can be self-consistently arranged in space. There are 230 unique
manners in which this can be done and, thus, 230 space groups.
Space groups add the centering information and microscopic
elements to the point groups.
Schematically, the relationship between the 7 crystal systems, 14
Bravais Lattices, 32 point groups, and 230 space groups are as
follows:
14 Bravais
Add centering
lattices
7 crystal
systems
230 space
groups
Add macroscopic symmetry

Use microscopic symmetry
above minimum
32 point
groups
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Introduction-12
Crystal structure
Summary
Lattice must be invariant under point symmetry operations
Places restriction on primitive translation vectors, when all operations considered to be
applied through a lattice point
This leads to space lattices or Bravais lattice
Microscopic symmetry operations like glide and screw add more Bravais lattices both
in 2d and 3d
Familiarity with notations used
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Crystal structure
Summary
A space group is a representation of the ways that the
macroscopic and microscopic symmetry elements (operations)
can be self-consistently arranged in space. There are 230 unique
manners in which this can be done and, thus, 230 space groups.
Space groups add the centering information and microscopic
elements to the point groups.
Schematically, the relationship between the 7 crystal systems, 14
Bravais Lattices, 32 point groups, and 230 space groups are as
follows:
14 Bravais
Add centering
lattices
7 crystal
systems
230 space
groups
Add macroscopic symmetry

Use microscopic symmetry
above minimum
32 point
groups
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Introduction-13
PROBLEMS FROM CRYSTAL STRUCTURE

Discuss the symmetry elements of the 2d space group p3m1 and
show the positions in a 2d lattice.)
Point Group 3m
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Problem
Primitive lattice of the bcc and fcc
a
a1
i j k
2
a
a2
i j k
2
a
a3
i j k
2
a
a1
i j
2
a
a2
j k
2
a
a3
i k
2
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Introduction-14
CLOSED PACKING 2D
Square lattice:Packing efficiency
R2
Area of circle
=
=
= 0.785
4R2
Area of square
Triangular lattice (best close pack)
R2
Area of circle
=
=
= 0.907
Area of hexagon 2 3 R2
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Close-Packed Structures
The crystal structures of a large number of metals, alloys and inorganic
compounds can be described geometrically in terms of a close-packing
of equal spheres, held together by interatomic forces
Frequently, the positions of one kind of atoms of ions in inorganic
structures correspond approximately to those of equal spheres in a closepacking with the other atoms distributed among the voids
All such structures are referred as close-packed structures though they
may not be ideally close-packed
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Introduction-15
Voids and closed pack structures

closed packing -- equidimensional objects arranged to fill space
efficiently
Packing efficiency =
volume occupied by atoms

total volume of the crystal
The volume not occupied by atoms is void space, or voids

The size of the void is indicated by the largest sphere that can be fit
inside it
The coordination number of a void is the number of atoms that
immediately surround it
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The close-packed arrangement of equal spheres in a plane is shown
where each sphere is in contact with six other spheres. Since the
symmetry of this layer is 6mm , such a layer is called a hexagonal closepacked layer
Let this layer be called an A layer. It contains two types of triangular
voids, one with the apex of the triangle upwards in the diagram and
labeled B, and the other with the apex downwards and labeled C
In 2 d unit cell indicated a=b, =1200
Coords of A, B and C are
(0,0), (1/3, 2/3) and (2/3, 1/3) respectively
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Introduction-16
In a three-dimensional packing the next hexagonal close-packed layer of
spheres can occupy either the sites B or C, but not both. Similarly the
layer above a B layer can be either C or A and that above a C layer either
A or B. No two successive layers can be alike
Any sequence of the letters, A B and C with no two successive letters
alike represents a possible manner of close-packing equal spheres
In such a three- dimensional close-packing, each sphere is surrounded by
and touches 12 other spheres. This is the maximum number of spheres
that can be arranged to touch a given sphere and it provides the
maximum packing density for an infinite lattice arrangement
The two most common close-packed structures which occur in nature
are: (i) the hexagonal close-packing (hcp) with a layer stacking ABAB..
and (ii) the cubic close-packing (ccp) with a layer stacking ABCABC
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Comparison of hcp and ccp structures
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Introduction-17

1
Show that the c/a ratio for an ideal hcp is 8/ 3.

x
x
y
a
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a 3
2
a
y
tan 30
2
c
2h
a
2 3
2 x2
y2
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CLOSED PACKING-3D
Simple cubic (a = 2R) touch along edges
Volume of one sphere
no. atoms per unit cell
unit cell volume
4 3
R
13 3
0.5236
8R
Body centred cubic ( 3a = 4R) touch along body diagonal
unit cell volume
4 3
R
2 3
0.6802
3
4R
3
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Introduction-18
CLOSED PACKING-3D
Face centred cubic ( 2a = 4R) touch along face diagonal
unit cell volume
4 3
R
4 3
0.7404
3
4R
Shown earlier
2
Hexagonal closed pack (a = 2R, c = 8a/ 3)
4 3
R
3
0.7404
2
1 3
8
2
2R
6
2R
3 4
3
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CLOSED PACKING-3D
Diamond (( 3a = 8R) touch along body diagonal
unit cell volume
4 3
R
0.3401
8 3
3
8R
3
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Introduction-19
Voids in closed pack structures

Larger atoms or ions occupy positions approximately corresponding to
those of equal spheres
Smaller atoms are distributed among the voids
Three- dimensional close-packings of spheres have two kinds of voids
Tetrahedral voids
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Octahedral voids
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Tetrahedral voids
If the triangular void in a close-packed layer has a sphere directly over it
a void with four spheres around it results
Tetrahedral void since the four spheres surrounding it are arranged on the
corners of a regular tetrahedron
If R denotes the radius of the four spheres surrounding a tetrahedral void,
the radius of the spheres that would just fit into this void is given by
0.225 R
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Introduction-20
Octahedral voids
If a triangular void pointing up in one close-packed layer is covered by a
triangular void pointing down in the adjacent layer a void surrounded by
six spheres results.
Octahedral void since the six spheres surrounding it lie at the corners of a
regular octahedron. The radius of the sphere that would just fit into an
octahedral void in a close-packing is given by 0.414 R
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voids
Location of voids relative to the atoms in fcc lattice
Atom of closed
packed structure
Octahedral void
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tetrahedral void
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Introduction-21
voids
Voids in bcc lattice (a) octahedral voids (b) tetrahedral voids
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voids
Voids in fcc lattice (a) octahedral voids (b) tetrahedral voids
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Introduction-22
voids
Voids in hcp lattice (a) octahedral voids (b) tetrahedral voids
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Distance between the atom at the centre of the interstice site and atoms
on the crystal lattice in terms of the lattice constant
fcc lattice ( 2a = 4R)
R r
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3
4
r
R
2
2
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Introduction-23
voids
To determine number of tetrahedral and octahedral voids
A sphere in a hexagonal close-packed layer A is surrounded by three B
voids and three C voids
One layer is placed on top of this and another layer below this
In each layer three voids of one kind (say B) are occupied and the other
three (say C) are not. Thus the three B voids become tetrahedral voids
and the three C voids become octahedral voids - Total 2 X 3=6
B
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voids
The particular sphere being considered covers a triangular void in the
layer above it and another in the layer below it. Thus two more
tetrahedral voids surround the spheres
Total octahedral voids = 6 Tetrahedral voids =8
A tetrahedral void is shared by four spheres
An octahedral void is shared by six spheres
Number of tetrahedral voids = 8/4 = 2 X number of spheres
Number of octahedral voids = 6/6 = number of spheres
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Introduction-24
Voids -summary
Tetrahedral void is made of four atoms 3in one plane and 1 above them.
Octahedral void is made of 6 atoms 4atoms in one plane and one above
and one below
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Voids Coordination number

Number of nearest neighbours (NN) depends on ratio of size of atoms.
For an atomic radii ratio r/R=0.2, the greatest possible number of
neighbours is 3
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Introduction-25
Voids Coordination number

NN for different atomic radii ratios and resulting geometry
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Voids-critical radius ratio

Triangular void (NN=3)
LM
LO
r
R
R
R r
1
cos 300
cos 300
1 0.155
Tetrahedral void (NN=4)

LM
R
LP
2
LO R r LO
3
r
3
2
0.225
R
2
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Introduction-26
Voids-critical radius ratio

Octahedral void (NN=6)
LM
LN
r
R
2
1
2R r
2R
2 1 0.414
bcc void (NN=8)

LM
LN
r
R
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3
1
2R r
2R
Body diagonal
3 1 0.732
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Voids and chemical formula

Depending on the close packing and void occupied by atoms/ions, the
formula of the compound can be obtained
Example 1:
Atom A forms the close packing and B occupies all the tetrahedral voids
Formula xA:2xB = AB2
Example 2:
Atom B forms the close packing, A occupies half the tetrahedral void
and C occupies all the octahedral void
Formula: BAC
Example 3:
Atom A forms the close packing and B occupies 2/3rd the tetrahedral void
Formula: A3B4
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Introduction-27
Voids and chemical formula

Some crystal structures described in terms of closed packing of anions
Crystal structure Anion packing Fraction of cations occupied
NaCl, Mgo
K2O
ZnS (Sphalerite)
ZnO (wurzite)
NiAs
-Al2O3
CdCl2
CdI2
Li2O (Antifluorite)
CaF2 (Fluorite)
FCC
FCC
FCC
HCP
HCP
HCP
FCC
FCC
FCC (CCP)
FCC (cations)
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All octahedral
All tetrahedral
All upright tetrahedral
All upright tetrahedral
All octahedral
Two-thirds octahedral
One half octahedral (alternate layer)
One half octahedral (alternate layer)
All tetrahedral
All tetrahedral (anions)
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Common crystal structures

Face-centered cubic (FCC) -- 1 atom/lattice point (4
atoms per unit cell)
FCC translations: 000, 0, 0, 0
conventional unit cell
space-filling model
Examples: Cu, Ni, Au, Ag, Pb

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Introduction-28

Hexagonal close packed (HCP) -- 2 atom/lattice
point (2 atoms per unit cell)
space-filling model
Examples: Zn, Mg, Be, -Ti
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CsCl -- variant on
the primitive cubic
NaCl -- variant on
the face-centered
cubic
plus FCC
Na+ at 000
Cl at 00
translations
Cs+ at 000
Cl- at
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Introduction-29

Body-centered cubic (BCC) -- 1 atom/lattice point (2
atoms per unit cell); not a close-packed structure
space-filling model
Examples: -Fe, Cr, Mn V
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The diamond crystal structure

The diamond crystal structure is FCC with a two-atom
111
basis (000 and 4 4 4 + FCC translations)
Each atom is surrounded by four identical nearest
neighbors in a tetrahedral arrangement
Examples: Si (5 1022 cm-3), Ge, -Sn (group IV elements)
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Introduction-30
The zincblende crystal structure

Like diamond, the zincblende structure is FCC with a twoatom basis, but the atoms are different types
Each A-atom is surrounded by four B-atom nearest
neighbors in a tetrahedral arrangement
Commonly seen in stoichiometric compound semiconductors; GaAs, CdTe, ZnSe
Tetrahedral
coordination
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The wrtzite crystal structure

The wrtzite structure is a hexagonal variant of the
zincblende structure in which the stacking order of the A-B
tetrahedra is varied
Examples: GaN, CdS, AgI
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Introduction-31
PACKING FRACTION
At 0K an ideal crystal(AB) with NaCl structure consists of a cubic closed
packing of B- occupying the octahedral sites. If the A+ touch the B- ions
and B- ions touch each other, what will be the fraction of the volume
occupied in the unit cell
2
fraction
4
3

unit cell volume
rA3 rB3
a3
0.793
2a = 4rB, rA+rB=a/2
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THEORETICAL DENSITY
POLYCRYSTALLINE SOLIDS
The density of a material is often determined pycnometrically. This gives the

macroscopic density. Porosity (voids, pores between grains/ crystallites) and
contaminants will contribute to the measured density being smaller than the theoretical
value for the material if it was perfect and built in three dimensions from the atomic
arrangement found in the unit cell. Using X-ray diffraction it is possible to obtain
information about the unit cell dimensions. The so-called X-ray density is the
theoretical density calculated from the crystallographic data for the unit cell, i.e. for a
perfect material
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Introduction-32
THEORETICAL DENSITY
Density calculated from the volume of the crystal
Let Z = number of molecule (formula units) in one unit cell
Mw = molecular weight of the material
a = lattice constant
N0 = Avogadross number
= density of the material
Then
[kg / m 3 ]
Z [molecules]Mw[kg / kmoles]
N 0 [molecules / kmole]a 3[m 3 ]
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THEORETICAL DENSITY
1
A certain fcc metal has a lattice constant of 0.35 nm. If its density is
9000 kg/m3, find its atomic weight?
For fcc Z = 4. Substituting the given data in equation below gives atomic
weight (molecular wt for monoatomic system) = 58.193
[kg / m 3 ]
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Z [molecules ]Mw[kg / kmoles ]

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Introduction-33
THEORETICAL DENSITY
2
The density of a solid with NaCl structure is 2100 kg/m3. A single

crystal cube of the material weighs 0.029 kg. What is edge length of
the cube. If the nearest neighbour distance in this system is 0.3 nm,
how many pairs of A-B ions will be present along any edge of the
cube. What will be the molecular weight of 1 formula unit (AB)
[kg / m 3 ]
2100[kg / m3 ]
Z [molecules]Mw[kg / kmoles]
4[molecules]Mw[kg / kmoles]
N 0 [molecules / kmole] 0.6 10
2100[kg / m3 ]
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9 3
[m3 ]
0.029kg
L3[m3 ]
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THEORETICAL DENSITY
3
A polycrystalline solid has a spinel structure (cubic symmetry) with 8

formula units in a unit cell. If the molecular weight is 231.55 and
lattice constant as determined from XRD is 0.841 nm, calculate the X
ray density. The observed density is 5000 kg/m3. Calculate the
percentage porosity.
[kg / m 3 ]
8[molecules]231.55[kg / kmoles]
N 0 [molecules / kmole] 0.841 10
9 3
[m3 ]
[kg / m3 ] 5170[kg / m 3 ]
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Introduction-34
Model for binary compounds

Two simple models for representing binary compounds AC with FCC
structure with atom A at 0 0 0 and C at 1 1 1
444
Ionic model: Cn+ An- : FCC of large anions An- and small cations Cn+ at
tetrahedral sites of anion FCC lattice. If anions touch each other, their
radii = a0 = 2 a/4. Radius of tetrahedral void = aT = ( 3- 2) a0 / 2,
where a is the lattice parameter
If a0 <aT, closed pack structure is formed (e.g Al3+ in AlSb)
If a0 >aT, cations push the larger anions apart
No closed pack structure
Packing of larger S atoms and smaller Zn atoms in
zincblende structure. Each atom is centred in a tetrahedron
of the other atom type
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Model for binary compounds

Ionic model: Cn+ An- : FCC of large anions An- and small cations Cn+ at
tetrahedral sites of anion FCC lattice. For purely ionic model,
ACionic = r(Cn+)+r(An-), where r is ionic radii
Covalent model: Neutral atoms A and C. Their atomic radii must be
comparable. For purely covalent model, ACcovalent = r(C)+r(A)
Distance AClattice =
3 a/4, where a is lattice constant
Check whether AClattice is equal to ACionic or ACcovalent

for various binary compounds
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Introduction-35
Atomic and ionic radii

For several elements found in semiconductors (in nm)
Group
Atomic number
Atom
Radius
Ion
Radius
II
30
Zn
0.133
Zn2+
0.074
II
48
Cd
0.149
Cd2+
0.097
II
80
Hg
0.151
Hg2+
0.110
III
13
Al
0.143
Al3+
0.051
III
31
Ga
0.122
Ga3+
0.0602
III
49
In
0.163
In3+
0.081
IV
14
Si
0.118
IV
32
Ge
0.123
15
0.110
P3-
0.212
33
As
0.124
As3-
0.222
51
Sb
0.145
Sb3-
0.245
VI
16
0.101
S2-
0.284
VI
34
Se
0.113
Se2-
0.191
VI
52
Te
0.143
Te2-
0.211
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Comparison of compounds
nn distance for semiconductors (in nm). For comparison data for some
alkali halides and alkaline earth chalcogenicide is also shown
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Compound
AClattice
ACionic
ACcovalent
Compound type
ZnS
0.234
0.258
0.231
Semiconductor
AlP
0.236
0.263
0.253
Semiconductor
GaAs
0.245
0.284
0.246
Semiconductor
CdS
0.252
0.281
0.247
Semiconductor
HgTe
0.279
0.321
0.294
Semiconductor
InSb
0.281
0.326
0.308
Semiconductor
MgO
0.211
0.198
0.232
Alkaline earth chalcogenicide
CaS
0.285
0.283
0.299
SrSe
0.301
0.303
0.419
NaCl
0.282
0.278
0.350
Alkali halide
KBr
0.353
0.353
0.404
Alkali halide
RbI
0.367
0.367
0.419
Alkali halide
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Introduction-36
Comparison of compounds
Results from Table
For alkali halides and alkaline earth chalcogenicide fit the ionic model
very well
For semiconductors neither model fits the data but covalent model is
closer to agreement
It can be shown that for all the semiconductors listed in the Table the
fractional covalency ~0.68
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Crystal structure of materials

Metals:
Mostly homopolar Predominantly bcc, fcc or hcp
Ceramics:
Mostly heteropolar e.g Metal/ ligand. Structure depends on relative size
of atoms forming the compound
In case of covalent bonded solids, there is strong dependency of the
bonding on crystallographic direction. Glasses (amorphous) phase
favoured in some cases. E.g SiO2
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Introduction-37

Polymers:
The chain structure of polymers has tendency to generate ordered
structures
hydrogen bond formation owing to van der Waals interaction
Order obtained by folding the polymer chains to establish periodic
molecular arrangements space lattice
Unit cell contains >50 atoms, corresponding symmetry low
E.g Polyethylene (folded chain) and Nylon triclinic (lowest symmetry)
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Polymers:
(a) Schematic representation of chain structure of polyethylene
(b) Folded polymer chains in planes of crystalline polythylene
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Introduction-38

Polymers:
Unit cell of nylon 66 with molecules arranged in a triclinic unit cell
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Structure of nanoparticle clusters

Most metals form c-p lattice
Ag, Al, Au, Pb, Pt and Rh: fcc (ccp)
Mg, Nd, Os, Re, Ru, Y and Zn: hcp
A number of other metals: bcc (not so closely packed)
Some have change in structure with temperature
Generally crystal structure of large nanoparticles is same as bulk
structure with possibly different lattice parameters
In many cases it is observed that nanoparticles with dia < 5nm
may have different crystal structure
For example 3-5 nm gold particles have icosahedral structure
rather than fcc in the bulk
It is therefore of interest to study stability of clusters
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Introduction-39

Atomic clusters show an interesting phase of matter between
solids and molecules and represent increasing potential for
technological applications
Their structure and energetics have been the focus of many
experimental and theoretical studies
Clusters containing a few thousands of atoms consist of an
intermediate regime between individual atoms and the bulk solids
In this regime, the physical and chemical properties of clusters are
size-dependent
Thus, clusters act as a bridge for a detailed understanding as to
how matter evolves from atoms to bulk
An approximate classification according to the number of atoms:
1 to 10 atoms
molecules
10 to 106
nanoparticles
>106
bulk
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1 to 10 atoms
molecules:
These also very complicated to analyse from first principles
Need to understand quantum mechanics and molecular dynamics
Quantum mechanics for many body problem utilizes Density
functional theory
Theory that captures the particle wave duality of matter
Applies in microscopic realm- length and time scale relevant to
sub-atomic particles like electrons and nuclei
When properties of Physical objects (solids, clusters and
molecules) studied at resolution at which atomic degrees of
freedom are explicitly involved, quantum mechanics becomes
necessary
Basic quantum mechanics relevant to study of solids, clusters and
molecules presented here
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Introduction-40

To study the physics of solids, one needs to solve the quantum
mechanical problem -Schrodinger equation, described by its
Hamiltonian, where multiple electrons interact with multiple nuclei
H
l
pl2
2M l
1
2l
ql ql
Rl Rl
U ri , rj
i 1
Terms: K.E, P.E between electron-nuclei, P.E between electrons

Before going further let us review quantum mechanics briefly
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Quantum History
Planck/Einstein: Energy is absorbed and
emitted in quantum packets of energy
related to the frequency of the radiation,
f, by E=hf where h= 6.63 10 34 J-s.
(often use =2 f and
=h/ (2 )).
De Broglie: The position of freely
propagating electrons can be predicted by
associating a wave with them of
wavelength =h/mv
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Introduction-41
Wavelike behavior:
Waves diffract and waves interfere

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How can Particles Interfere?

In fact things only appear to be particles
or waves on macroscopic scales. Our
intuition about nature is wrong at the
atomic scale:
(Courtesy of Dr. Akira Tonomura)

6-Feb-14
http://www.hqrd.hitachi.co.jp/em/doubleslit-f1.cfm
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Introduction-42
The key point of Quantum Mechanics

Particle behavior can be predicted only in terms of
probability
Quantum mechanics provides the tools for making
probabalistic predictions
The predicted particle distributions are wavelike
The DeBroglie wavelength associated with probability
distributions for macroscopic particles is so small that
quantum effects are not apparent.
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Measurement in the two slit experiment

what happens if we measure the particles
path?
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sin
n
d
sin

Lindsay 2008
84
nh
dpe
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Introduction-43
Measurement in the two slit experiment

p
h
d
Laser Microscope Measurement
Momentum of
a photon:
Momentum
required to
resolve slits:
Angle by which
electron is
deflected:
h
,p
p
p
sin
E
c
h
d
1
h
dpe
Exactly the first order diffraction angle!

Lindsay 2008
85
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The Uncertainty Principle
x p
h
4
E t~h
A particle confined to a tiny volume

must have an enormous
momentum. e.g., the groundstate of
a hydrogen atom.
The uncertainty in energy of a
particle observed for a very short
time can be enormous.
Plancks constant 6.626 10-34Js
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Introduction-44

h
4
x p
A particle confined to a tiny volume

must have an enormous
momentum. e.g., the groundstate of
a hydrogen atom.
Speed of electron confined to hydrogen atom

p ~ h/4 x = 5.27 X 10 -25 kg m/s
With m = 9.1 X 10 -31 kg we get
v = 5.8 X 105 m/s
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h
4
x p
Hitachi experiment revisited
The discussion on electrons path can be recast

using uncertainty in position and momentum,
where z is the diatance between the biprism
and screen. The uncertainity in momentum ~
angular difference between direction of beams
emerging from source 1 to source 2 multiplied
by incident momentum
x
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hz
pe d
pe d
z
x p
h
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Introduction-45
Rules of Quantum Mechanics

(single particle)
Replace probability with probability

amplitude a complex number
Probability amplitude for 2 sequential
events = product of amplitudes for each
Probability amplitude for 2 paths = sum
of amplitudes for each path
Probability is square of probability
amplitude.
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Quantum vs. Classical

CLASSICAL: Add probabilities
for 2 paths
QUANTUM: Add (complex)
amplitudes and square
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Introduction-46
Wavefunctions
The values of probability amplitude at all
points in space and time are given by a
Wavefunction
(r, t).
Systems that do not change with
time are called stationary:
(r).
Lindsay 2008
91
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Wavefunctions
Since the particle must be somewhere:
*
(r ) (r )d 3r 1
r
Note the rule for making a product of complex
variables!
In the shorthand invented by Dirac this
equation is:
1
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Introduction-47
Quantum weirdness identical and

non-identical particles
Consider an experiment where two particles
are scattered, as envisaged in the center of
mass frame of reference:
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Identical particles and adding

wavefuntions
2
The measured quantity is
So the same probability could be
obtained with either sign of
i.e.
When we consider adding probability
amplitudes for two different particles,
we need to consider both possible signs
of the wave function.
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Introduction-48
Wavefunctions for identical particles

In fact, there are two types of particles:
Fermions: The wave functions for
having the particles in the same state
are subtracted.
Bosons: the wavefunctions for having
the particles in the same state are
added.
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The scattering experiment with

quantum mechanics
Two ways that a particle can enter a given

detector
We have to add the wavefunctions for each case
and square to get the probability
For simplicity, we will consider 90 scattering,
= /2
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Introduction-49
Two non identical particles
Suppose that the particles were prepared in different

spin states, and the detectors were spin sensitive, so
that you could tell which particle enters which detector
Then there are only two possibilities, e.g., particle 1 is
scattered into D1, or particle 2 is scattered into D1:
P(D1) = | ( )|2 + | ( - )|2 . For = /2 ,
P(D1) = 2 2( /2)
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Two identical particles (Bosons)
Now the two types of event become

indistinguishable. We have to add the
probability amplitudes:
P(D1) = | ( ) + ( - )|2. For = /2:
P(D1) = 4 2( /2)
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Introduction-50
Two identical particles (Fermions)
Now the two types of event become

indistinguishable. We have to subtract the
probability amplitudes:
P(D1) = | ( ) - ( - )|2. For = /2:
P(D1) = 0
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Three outcomes in quantum

mechanics!
Distinguishable particles P(D1) = 2 2( /2)

(classical result)
Indistinguishable Bosons : P(D1) = 4 2( /2)
Indistinguishable Fernions: P(D1) = 0
The probabalistic nature of outcomes in quantum
mechanics changes things drastically!
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Introduction-51
Pauli Exclusion Principle

Consider 2 identical particles, particle 1 in state
particle 2 in state
2
The state could just as well be particle 1 in state
particle 2 in state 1
Thus the 2 particle wavefunction is
2
total
(1)
( 2)
(2)
(1)
+ for Bosons, - for Fermions
Two identical Fermions cannot be found in the

same state
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Bosons and fermions

Fermions are particles with odd spins, where the
quantum of spin is
Electrons have spin
3He nuclei have spin
and are Fermions
3
and are Fermions
2
4He nuclei have spins 4 and are Bosons

2
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Copyright (c) 102

Stuart Lindsay 2008
Aiyar, CRNTS
2/6/2014
Introduction-52
The Schrdinger Equation

Newtons Law for probability
amplitudes:
2
( x, t )
U ( x , t ) ( x, t ) i
2
x
2m
( x, t )
dt

Lindsay 2008
103
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Time independent Schrdinger Equation
If the potential does not depend upon

time, the particle is in a stationary
state, and the wavefunction can be
written as the product ( x, t ) ( x) (t )
putting this into the Schrdinger
equation gives
2
2m
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( x)
x2
U ( x) ( x)
1
i
(t )
(t )
dt

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Introduction-53
1
(t )
(t ) dt
i
i
(t )
dt
E (t )
const.
(t )
E
exp
E
t
i
So the angular frequency

of a probability wave in
a constant potential obeys E
and
( x, t )
( x) exp
iE
Note that the probability is NOT a function of time!

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2
2m
( x)
x2
U ( x) ( x)
H ( x)
E ( x)
E ( x)
H is called the Hamiltonian operator
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Introduction-54
ELEMENTS OF QUANTUM MECHANICS

Even though solving for wave function is viewed as fundamental
problem of quantum mechanics, wave function cannot be directly
observed
Parameter that can be measured for a system with N electrons is
the probability that these electrons are at r1, r2, .. rN,
respectively. This is given by the density of electrons
nr
*i r
Density functional theory uses this density instead of the wave

functions to solve Schrodinger equation
The problem reduces to solving a set of equations in which each
equation involves a single electron
A self consistent method used to solve the equations
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Many-electron quantum mechanics

without wavefunctions?
Density functional theory (DFT)
Hohenberg and Kohn: Ground state

energy is a unique functional of the
electron density distribution, n(r),
Get n(r) by minimizing E[n(r)]:
Enr
n(r )
The functional exists, but is not known,

so approximations are used
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Introduction-55
Example of an energy functional

E[n(r )] C n(r ) 5 / 3 dr
1
2
n(r1 )n(r2 )
dr1 dr2
r12
n(r )V (r )dr
XC
Kinetic energyCoulomb energy

(e-e)
Other
Exchange
potential
and
(e.g.,
correlation
nuclear)
In the Local Density Approximation, exchange
and correlation is modeled by n(r) 4/3
(Reprinted from Journal of Molecular Structure: THEOCHEM,
Volume 716, Ana-Maria Mendoza-Wilson
and Daniel Glossman-Mitnik,
"CHIH-DFT study of the electronic properties and
chemical reactivity of quercetin" Page 6,
Copyright 2005, with permission from Elsevier)
LUMO of quercetin
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Source: B K Agarwal et. Al: Journal of Nanoparticle Research 6: 363368,
2004
Investigated the lowest energy structures and structural and

electronic properties of small AgN (N = 110) clusters
Method used:Ab-initio self-consistent density functional method in
the local density approximation. binding energy, bond length and
the energy difference of HOMOLUMO states carried out in a
large energy interval for different isomeric forms of Ag clusters
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Introduction-56

Source: B K Agarwal et. Al: Journal of Nanoparticle Research 6: 363368,
2004
Optimised structure of AgN clusters

(Most stable is bold face)
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Molecular orbital calculations on 13 atom cluster (ccp has 12 nn) based
on the density functional approach predict that the icosahedral structure
has a lowest energy, suggesting the possibility of structural change
No experimental confirmation for Al (expt. Structure determination is
difficult)
A Yokozeki and G D Stien (J Appl. Phys. 49, 224 (1978)) studied clusters
of Bi, Pb, In and Ag
Indium clusters: > 6.5nm diameter fc tetragonl c/a ratio = 1.075
< 5.5nm strutural change c/a ~ 1 i.e fcc
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Introduction-57

13 atom microcluster cluster with different structures
FCC structure
hcp structure
icosahedral structure
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L.-L. Wang and D. D. Johnson, (Phys. Rev. B 75, 235405 2007)studied
clusters of Pt, Pd, and Rh
Used DFT with exchange correlation functional a plane-wave basis set
and projector augmented wave
13-atom isomers studied
Investigated total energy in eV relative to that of 13 single atoms
mean interatomic distance MIAD defined as
MIAD
1
prs
N prs
Rn
n 1
Here n runs over all pairs of atoms in the cluster and Rn is distance
between pair of atoms
MIAD : effective radius of cluster
first-principle MD to search for lowest-energy isomers
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Introduction-58

L.-L. Wang and D. D. Johnson, (Phys. Rev. B 75, 235405
2007)studied clusters of Pt, Pd, and Rh
Isomers of Pt13 cluster shown in the order of decreasing total energy.
Properties listed below the structure are in parentheses energy eV,
magnetic moment B/atom, mean interatomic distance , and in
brackets first nearest-neighbor coordination number, first NN
bond length and s-d hybridization index
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Isomers of Pd13 cluster shown in the order of decreasing total
energy. The properties listed below the structure are the
same as in earlier figure
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Introduction-59

Isomers of Rh13 cluster shown in the order of decreasing total
energy. The properties listed below the structure are the
same as in earlier figure
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All the clusters prefer low symmetry, open structures rather than high
symmetry, compact structures as might be expected for almost
filled d-band metals
For Pt13 both a stacked triangular structure and a square structure
combined with a tetrahedron have the lowest energy
For Pd13, a low-symmetry structure with relatively closed packing
has the lowest energy
For Rh13, a cubic structure with a maximum number of simple cubes
is found to be the lowest energy structure
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Lecture 03

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Introduction-1

Three dimensional Point Groups

Number of point groups: 32

Three dimensional Point Groups

Lattice Points per

Three dimensional Point Groups

Three dimensional Point Groups

Three dimensional Point Groups

C2, Cs, C2h

222, mm2, mmm

D2, C2v, D2h

C3, S6, D3, C3v, D3d

C6, C3h, C6h, D6, C6v,

C4, S4, C4h, D4,

23, m3, 432, 43m

International point group notation

Rotation inversion axis

Rotation axis with mirror plane normal to it

Rotation axis with diad axis(axes) normal to it

Rotation with mirror plane parallel to it

Rotation-inversion axis with diad axis normal

4/mmm Rotation axis with mirror planes normal and parallel to it

3 dimensional Bravais Lattice

The 14 Bravais Lattices

Three dimensional Space Groups

Three dimensional Space Groups

Rotation and inversion

Glide plane (Glide reflection)

to the Glide Plane

Glide plane (Glide reflection)

to the Glide Plane

(a) Mirror reflection

(a) Rotation diad axis 2

(a) Rotation triad axis 3

Three dimensional Space Groups

Three dimensional Space Groups

Add macroscopic symmetry

Add macroscopic symmetry

PROBLEMS FROM CRYSTAL STRUCTURE

Voids and closed pack structures

volume occupied by atoms

The volume not occupied by atoms is void space, or voids

PROBLEMS FROM CRYSTAL STRUCTURE

Show that the c/a ratio for an ideal hcp is 8/ 3.

Voids in closed pack structures

PROBLEMS FROM CRYSTAL STRUCTURE

Voids Coordination number

Voids Coordination number

Voids-critical radius ratio

Tetrahedral void (NN=4)

Voids-critical radius ratio

bcc void (NN=8)

Voids and chemical formula

Voids and chemical formula

Common crystal structures

conventional unit cell

Examples: Cu, Ni, Au, Ag, Pb

Common crystal structures

conventional unit cell

Examples: Zn, Mg, Be, -Ti

Common crystal structures

Common crystal structures

conventional unit cell

Examples: -Fe, Cr, Mn V