Periodicity of crystal

• A crystal posses long range order and

symmetry. The main property of crystal
structure is its periodicity. This periodicity
is due to the arrangement of atoms/molecules
in the lattice points. The crystal structure as a
whole can be considered as the repetition of
unit cell.
 Crystal lattices
• The crystal lattice is the symmetrical three-
dimensional structural arrangements of
atoms, ions or molecules (constituent particle)
inside a crystalline solid as points. It can be
defined as the geometrical arrangement of
the atoms, ions or molecules of the crystalline
solid as points in space.
• A crystal is a solid material that contains
atoms or groups of atoms arranged in a highly
ordered structure. This structural
arrangement is three-dimensional.
• A crystal lattice describes the arrangement of
these atoms in a crystal and characterized as
having translational symmetry.
 Unit Cell
• A unit cell is the smallest portion of a crystal
lattice that shows the three-dimensional
pattern of the entire crystal. A crystal can be
thought of as the same unit cell repeated over
and over in three dimensions. The figure
below illustrates the relationship of a unit cell
to the entire crystal lattice
 Bravais lattice
• In geometry and crystallography, a Bravais
lattice, named after Auguste Bravais (1850), is
an infinite array of discrete points generated
by a set of discrete translation operations
described in three dimensional space by. The
seven lattice systems and their Bravais lattices
in three dimensions.
• Bravais Lattice. Based on their Bravais lattices,
space groups and crystals are put into lattice
systems. There are seven different ways to
group the 14 Bravais lattices: triclinic,
monoclinic, orthorhombic, tetragonal,
rhombohedral, hexagonal, and cubic.
Bravias lattice
 Symmetry elements
• A symmetry element is a geometrical entity
about which a symmetry operation is
performed. A symmetry element can be a
point, axis, or plane. A symmetry operation is
the movement of a body (molecule) such that
after the movement the molecule appears the
same as before.
 Point group
• In geometry, a point group is a mathematical
group of symmetry operations (isometries in a
Euclidean space) that have a fixed point in
common.
• A Point Group describes all the symmetry
operations that can be performed on a
molecule that result in a conformation
indistinguishable from the original. Point
groups are used in Group Theory, the
mathematical analysis of groups, to determine
properties such as a molecule's molecular
orbitals
• In Schoenflies notation, point groups are
denoted by a letter symbol with a subscript.
The symbols used in crystallography mean the
following: Cn (for cyclic) indicates that the
group has an n-fold rotation axis. Cnh is Cn with
the addition of a mirror (reflection) plane
perpendicular to the axis of rotation.
 seven crystal systems
• Cubic
• Orthorhombic,
• Tetragonal
• Monoclinic,
• Triclinic,
• Rhombohedral and
• Hexagonal
 Triclinic: There exists only one type of triclinic
Bravais lattice, which is a primitive cell. It obeys the
following relationship. a ≠ b ≠ c
Monoclinic: Bravais lattices having monoclinic systems obey

𝞫 = 𝝲 = 90o and 𝛂 ≠ 90o

the following relations: a ≠ b ≠ c

The two possible types of monoclinic systems are primitive and

base centered monoclinic cells.
Orthorhombic systems: The Bravais lattices with obey the following
equations: a ≠ b ≠ c, 𝛂 = 𝞫 = 𝝲 = 90o

The four types of orthorhombic systems (simple, base centered, face-

centered, and body-centered orthorhombic cells) .

 are observed: a = b ≠ c , 𝛂 = 𝞫 = 𝝲 = 90o
Tetragonal Systems: In tetragonal Bravais lattices, the following relations

The two types of tetragonal systems are simple tetragonal cells and body-
centered tetragonal cells.
Hexagonal System :The only type of hexagonal Bravais lattice
is the simple hexagonal cell.

a = b ≠ c, 𝛂 = 𝞫 = 90o and 𝝲 = 120o

It has the following relations between cell sides and angles.
 Cubic System:

can be observed. a = b = c, 𝛂 = 𝞫 = 𝝲 = 90o

In Bravais lattices with cubic systems, the following relationships

The 3 possible types of cubic cells have been illustrated below.

 Rhombohedral System

is given by: a = b = c, 𝛂 = 𝞫 = 𝝲 ≠ 90o

Only the primitive unit cell for a rhombohedral system exists. Its cell relation
 Miller indices
• Group of three numbers that indicates the
orientation of a plane or set of parallel planes
of atoms in a crystal.
• The application of a set of rules leads to the
assignment of the Miller Indices (hkl), which
are a set of numbers which quantify the
intercepts and thus may be used to uniquely
identify the plane or surface.
 Miller Indices identification
• Step 1: Identify the intercepts on the x-, y- and z- axes.
• Intercepts: a, ∞, ∞
• Step 2: Specify the intercepts in fractional co-ordinates
• Fractional Intercepts: a/a, ∞/a, ∞/a i.e. 1, ∞, ∞
• Step 3: Take the reciprocals of the fractional intercepts
• The reciprocals of 1 and ∞ are 1 and 0 respectively,
thus yielding
• Miller Indices: (100)
 Atomic number

• The atomic number of an element is equal to

the total number of protons in the nucleus of
the atoms of that element. The atomic
number can provide insight into the electronic
configuration of the element. For example,
carbon has an electron configuration of [He]
2s2 2p2, since its atomic number is 6.
 Atomic number and mass number

• The number of protons and the number of

neutrons shall determine the mass number of
an element. Since the isotopes of an element
have slightly different mass numbers, it
calculates the atomic mass by obtaining the
mean of the mass numbers for its isotopes.
 Interplanar Spacing
• The interplanar spacing dhkl between
adjacent planes having Miller indices (hkl) is
defined as the distance between first such
plane from a parallel plane passing through
the origin.
• D-spacing?
• Associated with each plane is its d-spacing.
This is the distance between successive,
parallel planes of atoms.
 X-ray diffraction
• X-ray diffraction, phenomenon in which the
atoms of a crystal, by virtue of their uniform
spacing, cause an interference pattern of the
waves present in an incident beam of X-rays.
• XRD is the principal technique used to
investigate crystal structures in composite
materials in a nondestructive way: as known,
different crystal phases can lead to different
material properties.
 Bragg's Law
• Bragg's Law states the following: When the X-ray is
incident onto a crystal surface, its angle of incidence,
θ, will reflect with the same angle of scattering, θ. And,
when the path difference, d is equal to a whole
number, n, of wavelength, λ, constructive interference
will occur.
• Bragg’s diffraction was first proposed by William Henry
Bragg and William Lawrence Bragg, in 1913. Bragg’s
diffraction occurs when a subatomic particle
or electromagnetic radiation waves have wavelengths
that are comparable to atomic spacing in a crystal
lattice.
 Bragg Equation
• According to Bragg Equation:
• nλ = 2d sinΘ
• Therefore, according to the equation of Bragg’s Law:
• The equation explains why the faces of crystals
reflect X-ray beams at particular angles of incidence
(Θ, λ).
• The variable d indicates the distance between the
atomic layers, and the variable The variable d indicates
the distance between the atomic layers, and the
variable λ specifies the wavelength of the incident X-
ray beam and n as an integer.
 Atomic bonding
• All materials are made up of atoms. These
atoms are held together by forces called
interatomic bonds. The bonds act like springs,
linking each atom to its neighbour.
• There are three primary types of bonding:
• ionic
• covalent and
• metallic.
 Ionic bonding

• Ionic bonding is a form of chemical connection in

which one atom loses valence electrons and gains
them from another. For both atoms involved, this
exchange results in a more stable noble gas electrical
state. The attractive electrostatic interactions between
two ions of opposite charge form an ionic bond.
• When a positively charged ion forms a bond with a
negatively charged ion, one atom donates electrons to
the other, this is known as an ionic bond. The chemical
molecule Sodium Chloride is an example of an ionic
bond.
 Bond dissociation energy
• The bond dissociation energy is the energy
required—an endothermic process—to break a
bond and form two atomic or molecular
fragments, each with one electron of the original
shared.
• So triple bonds are stronger than doubles bonds,
which are stronger than single bonds. Therefore,
triple bonds have the highest dissociation energy,
whereas single bonds have the lowest
dissociation energy.
• A few examples of the endothermic process
are photosynthesis, evaporating liquids, melting ice,
dry ice, alkane cracking, thermal decomposition,
ammonium chloride in water and much more. As the
name implies, 'endo' means 'to absorb,' and 'thermic'
means 'heat.
• For example, dissociation of HO−H bond of a water
molecule (H2O) requires 118.8 kcal/mol (497.1 kJ/mol).
The dissociation of the remaining hydroxyl radical
requires 101.8 kcal/mol (425.9 kJ/mol). The bond
energy of the covalent O−H bonds in water is said to
be 110.3 kcal/mol (461.5 kJ/mol), the average of these
values.
• The three types of chemical bonds in order of
weakest to strongest are as follows: ionic
bonds, polar covalent bonds, and covalent
bonds. These types of bonds are determined
by the difference in electronegativity between
the bonded atoms.
 Cohesive energy
• The cohesive energy of a solid refers to the
energy required to separate constituent atoms
apart from each other and to bring them to an
assembly of neutral free atoms.
• In crystal: Metallic bonds. Cohesive energy is the
energy gained by arranging the atoms in a
crystalline state, as compared with the gas state.
Insulators and semiconductors have large
cohesive energies; these solids are bound
together strongly and have good mechanical
strength.
 Madelung constant
• The Madelung constant is used in determining
the electrostatic potential of a single ion in a
crystal by approximating the ions by point
charges. It is named after Erwin Madelung, a
German physicist.
• The Madelung constant is a property of the
crystal structure and depends on the lattice
parameters, anion-cation distances, and
molecular volume of the crystal.
• where r0 is the nearest neighbour distance,
and the Madelung constant of the ith ion is
given by the sum over all the other ions in the
crystal: Mi=∑jzjrij/r0.
• The Madelung constant for NaCl is about 1.75,
a value that is equal to the ratio of the energy
when a mole of crystal forms to that when a
mole of ion pairs forms.
• The Madelung constant, in this case, will be
defined by the summation: , where indicates
the sign of each term of the sum, and it is
positive if the ions have opposite electric
charges (attraction) and negative in sign if
they have an equal charge (repulsion), and + is
the sum of ionic radii of the ions in the lattice.
 Covalent bond
• A covalent bond is a chemical bond that
involves the sharing of electrons to form
electron pairs between atoms. These electron
pairs are known as shared pairs or bonding
pairs. The stable balance of attractive and
repulsive forces between atoms, when they
share electrons, is known as covalent bonding.
• A covalent bond is a bond where two or more
atoms share electrons. The sharing of atoms
helps complete the outer shell, or valence shell,
of both atoms. For example, oxygen has six
valence electrons. It can form a covalent bond
with two hydrogen atoms, each of which has one
valence electron.
• There are four major types of chemical bonds in
chemistry, which includes; Ionic bond, Covalent
bond, Metallic bond, and Hydrogen bond.
 Example
• Molecules that have covalent linkages include
the inorganic substances hydrogen, nitrogen,
chlorine, water, and ammonia (H2, N2, Cl2, H2O,
NH3) together with all organic compounds.
 Metallic bond
• Metallic bond, force that holds atoms
together in a metallic substance. Such a solid
consists of closely packed atoms. In most
cases, the outermost electron shell of each of
the metal atoms overlaps with a large number
of neighbouring atoms.
• Metallic bond' is a term used to describe the
collective sharing of a sea of valence electrons
between several positively charged metal
ions.
 Hydrogen bond
• Hydrogen bonding is a special type of dipole-
dipole attraction between molecules, not a
covalent bond to a hydrogen atom. It results
from the attractive force between a hydrogen
atom covalently bonded to a very
electronegative atom such as a N, O, or F
atom and another very electronegative atom.
• H-bond is primarily an electrostatic force of attraction
between a hydrogen (H) atom which is covalently
bonded to a more electronegative "donor" atom or
group (Dn), and another electronegative atom bearing
a lone pair of electrons—the hydrogen bond acceptor
(Ac). Such an interacting system is generally
denoted Dn−H···Ac, where the solid line denotes a
polar covalent bond, and the dotted or dashed line
indicates the hydrogen bond. The most frequent donor
and acceptor atoms are the period 2
elements nitrogen (N), oxygen (O), and fluorine (F).
Model of hydrogen bonds (1) between
molecules of water
 Van der Waals bond
• A weak attractive force between atoms or
nonpolar molecules caused by a temporary
change in dipole moment arising from a brief
shift of orbital electrons to one side of one
atom or molecule, creating a similar shift in
adjacent atoms or molecules.
•
 Van der Waals bond
• A weak attractive force between atoms or
nonpolar molecules caused by a temporary
change in dipole moment arising from a brief
shift of orbital electrons to one side of one
atom or molecule, creating a similar shift in
adjacent atoms or molecules.
 Crystal imperfections
• crystal defect, imperfection in the regular
geometrical arrangement of the atoms in a
crystalline solid. These imperfections result
from deformation of the solid, rapid cooling
from high temperature, or high-energy
radiation (X-rays or neutrons) striking the
solid.
• Line defects,
• Point defects,
• Volume defects,
• Surface defects.
• The crystal point defects type was first
regarded in the ionic crystals, but not in metal
crystals, which are much simpler.
 Line imperfection
• Any deviation from perfectly periodic
arrangement of atoms along a line is called
the line imperfection. A line defect is a lattice
distortion created about a line formed by the
solidification process, plastic deformation,
vacancy condensation or atomic mismatch in
solid solutions.
 Point imperfection
• Point defects are accounted for when the
crystallization process occurs at a very fast
rate. These defects mainly happen due to
deviation in the arrangement of constituting
particles. In a crystalline solid, when the ideal
arrangement of solids is distorted around a
point/ atom it is called a point defect.
 Crystal defects
• Point defects (vacancies, interstitial defects,
substitution defects)
• Line defect (screw dislocation, edge dislocation)
• surface defects (material surface, grain boundaries) .
• Substitutional – one atom is replaced by as different
type of atom.
• Interstitial – extra atom is inserted into the lattice
structure at a.
 Dipole moment
• A dipole moment arises in any system in
which there is a separation of charge. They
can, therefore, arise in ionic bonds as well as
in covalent bonds. Dipole moments occur due
to the difference in electronegativity between
two chemically bonded atoms.
•
• A dipole moment is the product of the magnitude
of the charge and the distance between the
centers of the positive and negative charges. It is
denoted by the Greek letter ‘µ’.
Mathematically,
• Dipole Moment (µ) = Charge (Q) * distance of
separation (r)
• It is measured in Debye units denoted by ‘D’. 1 D
= 3.33564 × 10-30 C.m, where C is Coulomb and m
denotes a metre.
 Atomic packing factor
• In crystallography, atomic packing
factor or packing fraction is the fraction of
volume in a crystal structure that is occupied
by atoms. It is dimensionless and always less
than unity.
• For practical purposes, the APF of a crystal
structure is determined by assuming that atoms
are rigid spheres. It is represented
mathematically by where N is the number of
atoms in the crystal and V is the volume. It can be
proven mathematically that one-component (one
type of atom) close-packed structures, those that
have the most dense arrangement of atoms, has
an APF of 0.74. In reality, this number can be
higher given specific intermolecular factors. For
multiple-component structures, the APF can
exceed 0.74.