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Crystal Geometry and Structure Determination

This document discusses crystal geometry and structure determination. It begins with a recap of concepts related to stability, entropy, and free energy. It then discusses thermally activated processes and kinetics, providing the Arrhenius equation. It defines the differences between crystalline and amorphous solids, noting crystals have long-range periodicity while amorphous solids are homogeneous and isotropic. It also discusses unit cells, lattice parameters, Bravais lattices, and the seven crystal systems in terms of their lattice structures.

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ABHINAV KUMAR SHUKLA
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© © All Rights Reserved
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48 views

Crystal Geometry and Structure Determination

This document discusses crystal geometry and structure determination. It begins with a recap of concepts related to stability, entropy, and free energy. It then discusses thermally activated processes and kinetics, providing the Arrhenius equation. It defines the differences between crystalline and amorphous solids, noting crystals have long-range periodicity while amorphous solids are homogeneous and isotropic. It also discusses unit cells, lattice parameters, Bravais lattices, and the seven crystal systems in terms of their lattice structures.

Uploaded by

ABHINAV KUMAR SHUKLA
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Lecture 3

Crystal Geometry
and
Structure Determination
Recap
Concept of stability and metastability

Internal energy

Specific heat

Enthalpy

Entropy: Thermal and configurational entropy

Free energy, Helmohltz energy

Condition of equilibrium
Thermally activated process
A + BC ---- AB + C
A + BC ---- (ABC)*---- AB + C
Atoms are oscillating ABC*
Energies are varying

H*
Rate n
E
H *
A + BC
Rate N exp
kT
Multiply by Av, no. gives AB + C
Arrhenius equation
Conf.
Kinetics
Arrhenius plot
Q
rate A exp
RT

ln (rate)

Q
slope
R

1
T
Difference between crystalline
and amorphous solids??
Crystals: long range periodicity, Anisotropic
Amorphous: Homogeneous, isotropic

Courtesy: H Bhadhesia
Crystal ?
A 3D translationally
periodic arrangement
of atoms in space is
called a crystal.
2D crystal
Note the facets
Translational Periodicity
Crystal
One can select a small volume of
the crystal which by periodic
repetition generates the entire
crystal (without overlaps or gaps)

Unit
Cell Space filling

Building block of
crystal
Few points about Unit cell
Unit cell is the imaginary, it doesn't really
exist: We use them to understand the
crystallography

It should be space filling, no gaps, no overlaps

We tend to choose unit cells with angles close


to 90 and shortest unit cell edge length
2D crystal

Unit cell of 2D crystal can be defined by two translation


vectors and angle between them
UNIT CELL:

The most common


shape of a unit cell is
a parallelopiped.
The description of a unit cell
requires:
1. Its Size and shape
(lattice parameters)

2. Its atomic
content
(fractional
coordinates)
Size and shape of the unit cell:
1. A corner as origin
2. Three edge vectors {a, b, c}
from the origin define
a a CRSYTALLOGRAPHIC
COORDINATE
SYSTEM
c 3. The three
lengths a, b, c and
the three
interaxial angles
b , , are called the
LATTICE PARAMETERS
7 crystal Systems
Crystal System Conventional Unit Cell
1. Cubic a=b=c, ===90
2. Tetragonal a=bc, ===90
3. Orthorhombic abc, ===90
4. Hexagonal a=bc, == 90, =120
5. Rhombohedral a=b=c, ==90
OR Trigonal
6. Monoclinic abc, ==90
7. Triclinic abc,
Lattice?
A 3D translationally
periodic arrangement
of points in space is
called a lattice.
Space Lattice

An array of points in space such that every point has identical


surroundings
lattices are infinite (infinite array)
Lattices have translational periodicity
or
Translationally periodic arrangement of points in space is called a lattice

We can have 1D, 2D or 3D arrays (lattices)


Lattice

a
Each lattice point in a lattice has identical neighbourhood
of other lattice points.
Similarly one can create 3D lattice as well
Crystal Lattice

A 3D A 3D
translationally translationally
periodic periodic
arrangement arrangement of
of atoms points
What is the relation between
the two?

Crystal = Lattice + Motif

Motif or basis: an atom or


a group of atoms associated
with each lattice point
Crystal=lattice+basis
Lattice: the underlying periodicity of
the crystal,
Basis: atom or group of atoms
associated with each lattice points
Lattice: how to repeat
Motif: what to repeat
Lattice + Motif = Crystal

+ =

Love Lattice + Heart = Love Pattern


Air,
Water
and
Earth
by
M.C.
Esher
Every
periodic
pattern
(and hence
a crystal)
has a
unique
lattice
associated
with it
Classification of lattice
The Seven Crystal System
And

The Fourteen Bravais Lattices


7 Crystal Systems and 14 Bravais Lattices

Crystal System Bravais Lattices


1. Cubic P I F
2. Tetragonal P I
3. Orthorhombic P I F C
4. Hexagonal P
5. Trigonal P
6. Monoclinic P C
7. Triclinic P

P: Simple; I: body-centred; F: Face-centred; C: End-centred


Side centred or base centred
Position of lattice points Effective
number of
lattice points
per cell
P 8 corners 1
I 8 corners + 1 body centre 2

F 8 corners + 6 face centre 4

C 8 corner + 2 centres of 2
opposite faces
Questions
Why we do not have 28 (7x4=28) Bravais
lattices?? We only have half of this!
Why some of them are missing??

What is the basis of classification?? Often


answer this by saying lattice parameter but
not true
Few points

14 Bravais lattices have 7 distinct symmetries

Based on symmetry we can assign them to distinct crystal


system
Lattices are
classified on the
basis of their
symmetry
What is
symmetry?
Symmetry

If an object is brought into self-


coincidence after some
operation it said to possess
symmetry with respect to that
operation.
Rotational Symmetries

Z
Angles:

180 120 90 72 60 45
Fold:
2 3 4 5 6 8
Graphic symbols
Reflection (or mirror symmetry)
Translational symmetry

Lattices also have


translational
symmetry

In fact this is the


defining symmetry of
a lattice

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