CHAPTER 2 ATOMIC STRUCTURE, INTERATOMIC BONDING AND STRUCTURE

OF CRYSTALLINE SOLIDS
2.1 Atomic Structure and Interatomic Bonding
2.1.1 Atomic Structure
Atoms are composed of electrons, protons, and neutrons. Electrons and protons are negative and
positive charged particles respectively. The magnitude of each charged particle in an atom is 1.6 ×
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10 Coulombs.

Figure 1: Schematic representation of the Bohr atom.

The mass of the electron is negligible with respect to those of the proton and the neutron, which
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form the nucleus of the atom. The unit of mass is an atomic mass unit (amu) = 1.66 × 10 kg, and
equals 1/12 the mass of a carbon atom. The Carbon nucleus has Z=6, and A=12, where Z is the
number of protons, and A the number of protons and neutrons. Neutrons and protons have very
similar masses, roughly equal to 1 amu each. A neutral atom has the same number of electrons and
protons, Z.
A mol is the amount of matter that has a mass in grams equal to the atomic mass in amu of the
atoms. Thus, a mole of carbon has a mass of 12 grams. The number of atoms in a mole is called the
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Avogadro number, Nav = 6.023 × 10 . Note that Nav = 1 gram/1 amu.
3 3
Calculating n, the number of atoms per cm of a material of density  (g/cm ):

n = N av
M
where M is the atomic mass in amu (grams per mol). Thus, for graphite (carbon) with a density 
= 1.8 g/cm3, M =12,
we get,
6 × 10 23 atoms/mol × 1.8 g/cm 3 22
n= = 9 × 10 C atoms/cm3.
12 g/mol

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For a molecular solid like ice, one uses the molecular mass, M ( H 2 O ) = 18. With a density of 1 g/cm3,
22 3
one obtains n = 3.3 × 10 H2O molecules/cm . Note that since the water molecule contains 3 atoms,
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this is equivalent to 9.9 × 10 atoms/cm3.
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Most solids have atomic densities around 6 × 10 atoms/cm3. The cube root of that number gives
the number of atoms per centimeter, about 39 million. The mean distance between atoms is the
inverse of that, or 0.25 nm. This is an important number that gives the scale of atomic structures in
solids.

2.1.2 Interatomic bonding in solids

In order to understand why materials behave like they do and why they differ in properties, it is
necessary that one should look at atomic level. The study primarily concentrates on two issues:
what made the atoms to cluster together, and how atoms are arranged. Atoms are bound to each
other by the number of bonds. These inter-atomic bonds are primarily of two kinds:
Primary bonds and Secondary bonds. Ionic, Covalent and Metallic bonds are relatively very
strong, and grouped as primary bonds, whereas van der Waals and hydrogen bonds are relatively
weak, and termed as secondary bonds. Metals and Ceramics are entirely held together by primary
bonds - the ionic and covalent bonds in ceramics, and the metallic and covalent bonds in metals.
Although much weaker than primary bonds, secondary bonds are still very important. They provide
the links between polymer molecules in polyethylene (and other polymers) which make them
solids. Without them, water would boil at -80°C, and life as we know it on earth would not exist.

Ionic Bonding: This bond exists between two atoms when one of the atoms is negative (has an
extra electron) and another is positive (has lost an electron). Then there is a strong, direct Coulomb
attraction. Basically, ionic bonds are non-directional in nature (the magnitude of the bond is equal
in all directions around an ion). An example is sodium chloride (NaCl). In the molecule, there are
more electrons around chlorine (Cl), forming Cl- and fewer electrons around sodium (Na), forming
Na+. Ionic bonds are the strongest bonds. In real solids, ionic bonding usually exists along with
covalent bonding.

Figure 2: Schematic representation of ionic bonding. Here, Na is giving an electron to Cl to have stable structure

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Covalent Bonding: In covalent bonding, electrons are shared between the atoms, to saturate the
valence. The simplest example is the H2 molecule, where the electrons spend more time in between
the nuclei of two atoms than outside, thus producing bonding. Covalent bonds are stereo-specific
i.e. each bond is between a specific pair of atoms, which share a pair of electrons (of opposite
magnetic spins). Typically, covalent bonds are very strong, and directional in nature. The hardness
of diamond is a result of the fact that each carbon atom is covalently bonded with four neighboring
atoms, and each neighbor is bonded with an equal number of atoms to form a rigid three-
dimensional structure.

Figure 3: Schematic representation of covalent bonding in Hydrogen molecule (sharing of electrons)

Metallic Bonding: Metals are characterized by high thermal and electrical conductivities. Thus,
neither covalent nor ionic bonding are realized because both types of bonding localize the valence
electrons and preclude conduction. However, strong bonding does occur in metals. The valence
electrons of metals also are delocalized. Thus, metallic bonding can be viewed as metal containing
a periodic structure of positive ions surrounded by a sea of delocalized electrons. The attraction
between the two provides the bond, which is non-directional.

Figure 4: Metallic bonding

Van der Waals Bonding; These include Fluctuating Induced Dipole bonds and Polar Molecule
Induced Dipole bonds.
Fluctuating Induced Dipole Bonds: Since the electrons may be on one side of the atom or the
other, a dipole is formed: the positive nucleus at the center and the electron cloud outside. Since
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the electron cloud moves, the dipole fluctuates. This fluctuation in one atom produces a fluctuating
electric field that is felt by the electrons of an adjacent atom. One atom then polarizes so that its
outer electrons are on the side of the atom closest to the positive side (or opposite to the negative
side) of the dipole in the adjacent atom.

Figure 5: Schematic representation of (a) an electrically symmetric atom and (b) an induced atomic dipole.

Polar Molecule-Induced Dipole Bonds: Another type of secondary bond exists with asymmetric
molecules, also called polar molecules because of positively and negatively charged regions e.g. a
permanent dipole moment arises from net positive and negative charges that are respectively
associated with the hydrogen and chlorine ends of the HCl molecule, leading to bonding. The
magnitude of this bond will be greater than for fluctuating induced dipoles.

Figure 6: Schematic representation of a polar hydrogen chloride (HCl) molecule.

The third type of secondary bond is the hydrogen bond. It is categorized separately because it
produces the strongest forces of attraction in this category.
Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as covalently
bonded hydrogen atoms – for example C-H, O-H, F-H – share single electron with other atom
essentially resulting in positively charged proton that is not shielded any electrons. This highly
positively charged end of the molecule is capable of strong attractive force with the negative end
of an adjacent molecule. The properties of water are influenced significantly by the hydrogen
bonds/bridges. The bridges are of sufficient strength, and as a consequence water has the highest
melting point of any molecule of its size. Likewise, its heat of vaporization is very high.

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 Figure 7: Schematic representation of hydrogen bonding in hydrogen fluoride (HF).

Figure 8: The arrangement of water molecules in (a) solid ice, and (b) liquid water.

2.2 Crystal structures, crystalline and Non-Crystalline materials

2.2.1 Crystal structures
All metals, a major fraction of ceramics, and certain polymers acquire crystalline form when they
solidify, i.e. in solid state atoms self-organize to form crystals. Crystals possess a long-range order
of atomic arrangement through repeated periodicity at regular intervals in three dimensions of
space. When the solid is not crystalline, it is called amorphous. Examples of crystalline solids are
metals, diamond and other precious stones, ice, graphite. Examples of amorphous solids are glass,
amorphous carbon (a-C), amorphous Si, most plastics.
There is very large number of different crystal structures all having long-range atomic order; these
vary from relatively simple structures for metals to exceedingly complex structures for ceramics
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and some polymers. To discuss crystalline structures it is useful to consider atoms as being hard
spheres, with well-defined radii. In this scheme, the shortest distance between two like atoms is
one diameter. In this context, use of terms lattice and unit cell will be handy. Lattice is used to
represent a three-dimensional periodic array of points coinciding with atom positions. Unit cell is
smallest repeatable entity that can be used to completely represent a crystal structure. Thus, it can
be considered that a unit cell is the building block of the crystal structure and defines the crystal
structure by virtue of its geometry and the atom positions within.

Figure 9: For the face centered cubic crystal structure, (a) a hard sphere unit cell representation, (b) a reduced-sphere
unit cell, and (c) an aggregate of many atoms.

Figure 10: For the body-centered cubic crystal structure, (a) a hard sphere unit cell representation, (b) a reduced-
sphere unit cell, and (c) an aggregate of many atoms.

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Figure 11: For the hexagonal close-packed crystal structure, (a) a reduced-sphere unit cell (a and c represent the short
and long edge lengths, respectively), and (b) an aggregate of many atoms.

Important properties of the unit cells:

• The type of atoms and their radii R.
• Cell dimensions (Lattice spacing a, b and c) in terms of R and
• Angle between the axis α, β, γ
• a*, b*, c* - lattice distances in reciprocal lattice , α*, β*, γ* - angle in reciprocal lattice
• n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells, we only
count a fraction of the atom, 1/m.
• CN, the coordination number, which is the number of closest neighbors to which an atom is
bonded.
• APF, the atomic packing factor, which is the fraction of the volume of the cell actually
occupied by the hard spheres.
Sum of atomic volumes
APF = ………………………………………Equation 2.0
Volume of cell.
Some very common crystal structures and relevant properties are listed in Table 2.1.
Table 2.1: Common crystal structures and their properties

Unit Cell n CN a/R APF

Simple Cubic 1 6 4/√4 0.52
Body-Centered Cubic(BCC) 2 8 4/√3 0.68
Face-Centered Cubic( FCC) 4 12 4/√2 0.74
Hexagonal Close Packed(HCP) 6 12 0.74

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EXAMPLE
Calculate the volume of an FCC unit cell in terms of the atomic radius R.

SOLUTION

In the FCC unit cell illustrated, the atoms touch one another across a face-diagonal the length of
which is 4R. Since the unit cell is a cube, its volume is a 3 , where a is the cell edge length.
From the right triangle on the face,
a 2 + a 2 = (4 R )
2

 a = 2R 2
The FCC unit cell volume FC may be computed from
VC = a 3
(
 VC = 2 R 2 )
3
= 16 R 3 2

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EXAMPLE
Show that the atomic packing factor for the FCC crystal structure is 0.74.
SOLUTION
The APF is defined as the fraction of solid sphere volume in a unit cell, or
volume of atoms in a unit cell V
APF = = S
total unit cell volume VC
Both the total atom and unit cell volumes may be calculated in terms of the
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atomic radius R. The volume for a sphere is π R 3 and since there are four atoms
3
per FCC unit cell , the total FCC atom(or sphere) volume is

VS = (4)  R 3 =
4 16
 R3
3 3
The total unit cell volume is VC = 16 R 3 2
16
 R3
VS 3
Therefore , APF = = = 0.74
VC 16 R 3 2
DENSITY COMPUTATIONS

Knowledge of the crystal structure of a metallic solid permits computation of its theoretical
density through the relationship below

………………………………………………………………………………..Equation 2.1

EXAMPLE

Copper has an atomic radius of 0.128 nm, an FCC crystal structure, and an atomic weight of 63.5
g/mol. Compute its theoretical density and compare the answer with its measured density.

SOLUTION
Since the crystal structure is FCC, n, the number of atoms per unit cell, is 4. Furthermore, the
atomic weight is given as 63.5 g/mol.
The unit cell volume for FCC is VC = 16 R 3 2
Where, R, the atomic radius, is 0.128 nm.
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Substitution for the various parameters into Equation 2.1;

The literature value for the density of copper is 8.94 g/cm3, which is in very close agreement with
the foregoing result.

2.2.2 Crystalline and Non-crystalline materials

Single Crystals: Crystals can be single crystals where the whole solid is one crystal. Then it has a
regular geometric structure with flat faces.

Figure 12: Photograph of a garnet single crystal

Polycrystalline Materials: Most crystalline solids are composed of a collection of many small
crystals or grains; such materials are termed polycrystalline. Various stages in the solidification of
a polycrystalline specimen are represented schematically in Figure 13. Initially, small crystals or
nuclei form at various positions. These have random crystallographic orientations, as indicated by
the square grids. The small grains grow by the successive addition from the surrounding liquid of
atoms to the structure of each. The extremities of adjacent grains impinge on one another as the
solidification process approaches completion. As indicated in Figure 13, the crystallographic
orientation varies from grain to grain. Also, there exists some atomic mismatch within the region
where two grains meet; this area is called a grain boundary.

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 Figure 13: Schematic diagrams of the various stages in the solidification of a polycrystalline material; the square
grids depict unit cells. (a) Small crystallite nuclei. (b) Growth of the crystallites; the obstruction of some grains that
are adjacent to one another is also shown. (c) Upon completion of solidification, grains having irregular shapes have
formed. (d) The grain structure as it would appear under the microscope; dark lines are the grain boundaries.

Non-Crystalline Solids: In amorphous solids, there is no long-range order. But amorphous does
not mean random, since the distance between atoms cannot be smaller than the size of the hard
spheres. Also, in many cases there is some form of short-range order. For instance, the tetragonal
order of crystalline SiO2 (quartz) is still apparent in amorphous SiO2 (silica glass).

Figure 14: Two-dimensional schemes of the structure of (a) crystalline silicon dioxide and (b) non-crystalline silicon
dioxide.

2.2.3 Grain size determination

The grain size is often determined when the properties of a polycrystalline material are under
consideration. The most common method utilized, is that devised by the American Society for
Testing and Materials (ASTM). The ASTM has prepared several standard comparison charts, all
having different average grain sizes. To each is assigned a number ranging from 1 to 10, which is
termed the grain size number. A specimen must be properly prepared to reveal the grain structure,

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which is photographed at a magnification of 100X. Grain size is expressed as the grain size number
of the chart that most nearly matches the grains in the micrograph.

Let n represent the grain size number, and N the average number of grains per square inch at a
magnification of 100X. These two parameters are related to each other through the expression

……………………………………………………..……………Equation 2.2

EXAMPLE
(a) Determine the ASTM grain size number of a metal specimen if 45 grains per square inch are
measured at a magnification of 100X
(b) For this same specimen, how many grains per square inch will there be at
a magnification of 85X?

SOLUTION
a) From Equation 2.2,

Taking logarithms of both sides of this expression leads to

b) At magnifications other than 100X, use of the following modified form of Equation 2.2 is
necessary.

…………………………………………….Equation 2.3

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2.3 Miller Indices and Anisotropy

2.3.1 Miller indices:

It is understood that properties of materials depend on their crystal structure, and many of these
properties are directional in nature. For example: elastic modulus of BCC iron is greater parallel
to the body diagonal than it is to the cube edge. Thus, it is necessary to characterize the crystal to
identify specific directions and planes. Specific methods are employed to define crystal directions
and crystal planes.

Methodology to define Point coordinates

The position of any point located within a unit cell may be specified in terms of its coordinates as
fractional multiples of the unit cell edge lengths ( i.e.,in terms of a, b, and c). To illustrate, consider
the unit cell and the point P situated therein as shown in Figure15.

Figure 15: The manner in which the q, r, and s coordinates at point P within the unit cell are determined. The q
coordinate (which is a fraction) corresponds to the distance qa along the x axis, where a is the unit cell edge length.
The respective r and s coordinates for the y and z axes are determined similarly.

We specify the position of P in terms of the generalized coordinates q, r, and s where q is some
fractional length of a along the x axis, r is some fractional length of b along the y axis, and similarly
for s. Thus, the position of P is designated using coordinates q r s with values that are less than or
equal to unity. Furthermore, we have chosen not to separate these coordinates by commas or any
other punctuation marks (which is the normal convention).

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EXAMPLE
For the unit cell shown in the accompanying sketch (a), locate the point having coordinates
1 1
1 .
4 2
SOLUTION
.

EXAMPLE
Specify point coordinates for all atom positions for a BCC unit cell.
For the BCC unit cell, atom position coordinates correspond to the locations of the centers of all
atoms in the unit cell—that is, the eight corner atoms and single center atom. These positions are
noted (and also numbered) in the following figure.
SOLUTION

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Methodology to define crystallographic directions in cubic crystal:
- A vector of convenient length is placed parallel to the required direction.
- The length of the vector projection on each of three axes are measured in unit cell dimensions.
- These three numbers are made to smallest integer values, known as indices, by multiplying or
dividing by a common factor.
- The three indices are enclosed in square brackets, [uvw]. A family of directions is represented
by <uvw>.

.
Figure 16: The [100], [110], and [111] directions within a unit cell.

For each of the three axes, there will exist both positive and negative coordinates. Thus, negative
indices are also possible, which are represented by a bar over the appropriate index. For example,
 
the 1 1 1 direction would have a component in the –y direction. Also, changing the signs of all

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    
indices produces an antiparallel direction; that is, 1 1 1 is directly opposite to 1 1 1 . If more
than one direction (or plane) is to be specified for a particular crystal structure, it is imperative for
the maintaining of consistency that a positive–negative convention, once established, not be
changed.

EXAMPLE
Determine the indices for the direction shown in the accompanying figure.

SOLUTION

EXAMPLE
 
Draw a 1 1 0 direction within a cubic unit cell.
SOLUTION

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Methodology to define crystallographic planes in cubic crystal:
- Determine the intercepts of the plane along the crystallographic axes, in terms of unit cell
dimensions. If plane is passing through origin, there is a need to construct another parallel plane
within the unit cell by an appropriate translation or a new origin must be established at the
corner of another unit cell.
- Take the reciprocals of these intercept numbers.
- Clear fractions.
- Reduce to set of smallest integers.
- The three indices are enclosed in parenthesis, (hkl). A family of planes is represented by {hkl}.

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 Figure 17: Representations of a series each of (a) (001), (b) (110), crystallographic planes.

EXAMPLE
Determine the Miller indices for the plane shown in the accompanying sketch (a).

SOLUTION

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EXAMPLE
( )
Construct a 0 1 1 plane within a cubic unit cell.

Why Miller indices are calculated in that way?

- Using reciprocals spares us the complication of infinite intercepts.
- Formulas involving Miller indices are very similar to related formulas from analytical
geometry.
- Specifying dimensions in unit cell terms means that the same label can be applied to any plane
with a similar stacking pattern, regardless of the crystal class of the crystal. Plane (111)
always steps the same way regardless of crystal system.

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2.3.2 Miller-Bravais indices
Miller-Bravais indices for determining direction
A problem arises for crystals having hexagonal symmetry in that some crystallographic
equivalent directions will not have the same set of indices. This is circumvented by utilizing a
four-axis, or Miller–Bravais, coordinate system as shown in Figure 18

Figure 18: Coordinate axis system for a hexagonal unit cell (Miller–Bravais scheme).

The three a1 , a 2 and a 3 axes are all contained within a single plane (called the basal plane) and
are at angles to one another. The z axis is perpendicular to this basal plane. Directional indices,
which are obtained as described above, will be denoted by four indices, as [uvtw]; by convention,
the first three indices pertain to projections along the respective a1 , a 2 and a 3 axes in the basal
plane. Conversion from the three-index system to the four-index system,

………………………………………………………………….Equation 2.4

Where, primed indices are associated with the three-index scheme and unprimed with the new
Miller–Bravais four-index system. Of course, reduction to the lowest set of integers may be
necessary, as discussed above. For example, the [010] direction becomes 1 2 1 0 .  

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EXAMPLE
Determine the indices for the direction shown in the hexagonal unit cell of sketch (a) below.

SOLUTION

Miller-Bravais indices for determining planes

For crystals having hexagonal symmetry, it is desirable that equivalent planes have the same
indices; as with directions, this is accomplished by the Miller–Bravais system shown in Figure
18. This convention leads to the four-index (hkil) scheme, which is favored in most instances,
since it more clearly identifies the orientation of a plane in a hexagonal crystal. There is some
redundancy in that i is determined by the sum of h and k through i = −(h + k ) . Otherwise, the
three h, k, and l indices are identical for both indexing systems.

EXAMPLE
Determine the Miller–Bravais indices for the plane shown in the hexagonal unit cell.
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SOLUTION

2.3.3 Anisotropy
It’s been agreed that many of the materials properties depend on the crystal structure. However,
crystals are not symmetric in all directions, or not the crystal planes same with respect to atomic
density/packing. Different directions in the crystal have different packing. For instance, atoms
along the edge of FCC crystals are more separated than along its face diagonal. This causes
properties to be different in different directions. This directionality of properties is termed as
Anisotropy.

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