CLL141-Introduction to materials

Atomic Structure
Hariprasad Kodamana
IIT DELHI

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Structure of materials at various
levels
macrostructure
Length-scale is ∼> 1, 00, 000 nm
Features that constitute macro-structure include porosity,
surface coatings, and such features as internal or external
micro-cracks
microstructure
length-scale of ∼ 10 − 1, 000 nm
Microstructure typically includes such features as average grain
size, grain size distribution, grain shape, grain orientation, and
other features related to defects in materials.
A grain is a small crystal of the material within which the
arrangement of atoms and repeats in a particular fashion in all
three dimensions.
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Structure of materials
Nano structure - the structure and properties of materials at a
nano-scale ∼ length-scale 1-100 nm)
short-and long-range atomic arrangements
Amorphous materials have only short-range atomic
arrangements while crystalline materials have short- and
long-range arrangements
In short-range atomic arrangements, the atoms or ions show a
particular order only over relatively short distances
For crystalline materials, the long-range atomic order is in the
form of atoms or ions arranged in a three- dimensional pattern
that repeats over much larger distances (from ∼> 100nm to up
to few cm).
atomic structure
how the atomic bonds lead to different atomic or ionic
arrangements in materials
The atomic structure includes all atoms and their arrangements,
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Atomic structure

The atomic number of an element is equal to the number of

electrons or protons in each atom
The mass of each proton and neutron is 1.67x 10−24 g
The mass of each electron is only 9.11 × 10−28 g
The atomic mass is equal to the average number of protons and
neutrons in the atom, is also the mass in grams of the Avogadro
number NA
The quantity NA is 6.02 × 1023 atoms/mol is the number of
atoms or molecules in a mole
An alternate unit for atomic mass is the atomic mass unit, or
amu, which is 1/12 the mass of carbon 12 (i.e., carbon atom
with 12 protons).

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Quantum numbers
The energy level to which each electron belongs is determined by
four quantum numbers.
Principal quantum number n: Discrete representation of electron
shell, with n increases, the electron is at a higher energy and is,
therefore, less tightly bound to the nucleus
Azimuthal quantum number l : describe the energy levels in each
quantum shell (subshell) ( l = 0 is s orbital, l = 1, p orbital, ..)
Magnetic quantum number ml : distinguish quantum states of an
electron (specific orbital or ”cloud” ) its angular momentum
along a given axis in space (ranges from −l to l)
Spin quantum number ms : that describes the intrinsic angular
momentum (or spin angular momentum, or simply spin) of an
electron with assigned values −1/2 and 1/2 reflecting different
electron spins
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Quantum numbers
The number of possible energy levels is determined by the first
three quantum numbers.
Orbitals: s − (2electrons), p − (6electrons), d − (10electrons),
f − (14electrons), g − (18electrons)
Electronic structure of an atom combines the numerical value of
the principal quantum number, the lowercase letter notation for
the azimuthal quantum number, and a superscript showing the
number of electrons in each orbital

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Valence and Electro-negativity
Usually, the valence is the number of electrons in the outer s
and p energy levels.
If an atom has a valence of zero, the element is inert
(non-reactive). An example is argon (Ar )
Other atoms prefer to behave as if their outer s and p levels are
either completely full, with eight electrons, or completely empty
Aluminum has three electrons in its outer s and p levels. An
aluminum atom readily gives up its outer three electrons to
empty the 3s and 3p levels
On the other hand, chlorine contains seven electrons in the outer
3s and 3p levels and will be accepting one electron
Electronegativity describes the tendency of an atom to gain an
electron.
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Electro-negativity and
Electro-positivity

Atoms with almost completely filled outer energy levels—such as

chlorine—are strongly electronegative
However, atoms with nearly empty outer levels such as
sodium—readily give up electrons and have low electronegativity
High atomic number elements also have low electronegativity
because the outer electrons are at a greater distance from the
positive nucleus, so that they are not as strongly attracted to
the atom
electropositive - an element whose atoms want to participate in
chemical interactions by donating electrons and are therefore
highly reactive - Eg: Lithium

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Atomic Bonding

Metallic bond
Covalent bond
Ionic bond
Van der Waals bond
In the first three of these mechanisms, bonding is achieved when
the atoms fill their outer s and p levels
These bonds are relatively strong and are known as primary
bonds
The van der Waals bonds are secondary bonds and originate
from a different mechanism and are relatively weaker

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Metallic bond

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Metallic bond
The metallic elements have more electro-positive atoms that
donate their valence electrons to form a sea of electrons
surrounding the atom
Aluminum, for example, gives up its three valence electrons,
leaving behind a core consisting of the nucleus and inner
electrons. Since three negatively charged electrons are missing
from this core, it has a positive charge of three
The valence electrons move freely within the electron sea and
become associated with several atom cores
The positively charged ion cores are held together by mutual
attraction to the electron, thus producing a strong metallic bond
Because their valence electrons are not fixed in any one position,
most pure metals are good electrical conductors of electricity at
relatively low temperatures
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Metallic bond

Materials with metallic bonding exhibit relatively high Young’s

modulus since the bonds are strong
Metals also show good ductility since the metallic bonds are
non- directional
Ductility refers to the ability of materials to be stretched or bent
without breaking
In general, the melting points of metals are relatively high

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Covalent bond

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Covalent bond
Materials with covalent bonding are characterized by bonds that
are formed by sharing of valence electrons among two or more
atoms
A silicon atom, which has a valence of four, obtains eight
electrons in its outer energy shell by sharing its electrons with
four surrounding silicon atoms
Each instance of sharing represents one covalent bond; thus,
each silicon atom is bonded to four neighboring atoms by four
covalent bonds
formed, the silicon atoms must be arranged so the bonds have a
fixed directional relationship with one another
A directional relationship is formed when the bonds between
atoms in a covalently bonded material form specific angles,
depending on the material
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Covalent bond
Covalent bonds are very strong resulting covalently bonded
materials are very strong and hard.
These materials also exhibit very high melting points
The materials bonded in this manner typically have limited
ductility because the bonds tend to be directional
The electrical conductivity of many covalently bonded materials
(i.e., silicon, diamond, and many ceramics) is not high since the
valence electrons are locked in bonds between atoms and are not
readily available for conduction
With some of these materials, such as Si, we can get useful and
controlled levels of electrical conductivity by deliberately
introducing small levels of other elements known as dopants (Eg:
conductive polymers)
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Ionic bond

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Ionic bond
When more than one type of atoms are present in a material,
one atom may donate its valence electrons to a different atom,
filling the outer energy shell of the second atom
Both atoms now have filled (or emptied) outer energy levels, but
both have acquired an electrical charge and behave as ions
The atom that contributes the electrons is left with a net
positive charge and is called a cation, while the atom that
accepts the electrons acquires a net negative charge and is called
an anion
The oppositely charged ions are then attracted to one another
and produce the ionic bond
For example, the attraction between sodium and chloride ions
produces sodium chloride (NaCl).
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Van der Waals Bonding
The origin of van der Waals forces between atoms and molecules
is quantum mechanical in nature
If two electrical charges p and q are separated by a distance d,
the arrangement is called a dipole and the dipole moment is
defined as q × d
When a neutral atom is exposed to an internal or external
electric field the atom gets polarized (i.e., the centers of positive
and negative charges separate), inducing a dipole moment
Polar molecules - the molecules, where the dipole moment does
not have to be induced—it exists by virtue of the direction of
bonds and the nature of atoms Eg. water
There are three types of van der Waals interactions, namely
London forces, Keesom forces, and Debye forces.
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Van der Waals Bonding

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Van der Waals Bonding
If the interactions are between two dipoles that are induced in
atoms or molecules, we refer to them as London forces (e.g.,
carbon tetrachloride)
When an induced dipole (that is, a dipole that is induced in
what is otherwise a non-polar atom or molecule) interacts with a
molecule that has a permanent dipole moment, we refer to this
interaction as a Debye interaction. An example of Debye
interaction would be forces between water molecules and those
of carbon tetrachloride.
If the interactions are between molecules that are permanently
polarized (e.g., water molecules attracting other water molecules
or other polar molecules), we refer to these as Keesom
interactions.
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Van der Waals Bonding

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Van der Waals Bonding
The bonding between molecules that have a permanent dipole
moment, known as the Keesom force, is often referred to as the
hydrogen bond, where hydrogen atoms represent one of the
polarized regions
Thus, hydrogen bonding is essentially a Keesom force and is a
type of Van der Waals force
Vann der Waals bonds are secondary bonds, which means bond
energies are smaller
Van der Waals forces between atoms and molecules play a vital
role in determining the surface tension and boiling points of
liquids.
Van der Waals forces provide an extra binding force between the
chains of these polymers
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Mixed bonding
In most materials, bonding between atoms is a mixture of two or
more types
Iron, for example, is bonded by a combination of metallic and
covalent bonding that prevents atoms from packing as efficiently
Compounds formed from two or more metals (intermetallic
compounds) may be bonded by a mixture of metallic and ionic
bonds (particularly when there is a large difference in
electro-negativity between the elements)
Any ceramic and semiconducting compounds, which are
combinations of metallic and nonmetallic elements, have a
mixture of covalent and ionic bonding
If △E is the he difference in electro-negativities, the fraction of
covalent bond can be computed by
Fraction covalent = exp(−0.25△E 2 ) (1)
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Binding energy and inter-atomic
spacing

Inter-atomic spacing is the equilibrium distance between atoms

results from a balance between repulsive and attractive forces
In the metallic bond, for example, the attraction between the
electrons and the ion cores is balanced by the repulsion between
ion cores
Equilibrium separation occurs when the total inter-atomic energy
(IAE) of the pair of atoms is at a minimum, or when no net
force is acting to either attract or repel the atoms

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Binding energy and inter-atomic
spacing

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Binding energy and inter-atomic
spacing

The interatomic spacing in a solid metal is approximately equal

to the atomic diameter, or twice the atomic radius r
We cannot use this approach for ionically bonded materials,
The binding energy, or the energy required to create or break the
bond
Consequently, materials having a high binding energy also have a
high strength and a high melting temperature
Ionically bonded materials have a particularly large binding
energy because of the large difference in electro- negativities
between the ions

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Binding energy and inter-atomic
spacing

Another property that can be linked to the binding energy is the

coefficient of thermal expansion (CTE)
The CTE describes how much a material expands or contracts
when its temperature is changed.
If a very deep interatomic energy (IAE) trough caused by strong
atomic bonding is characteristic of the material, the atoms
separate to a lesser degree resulting in a low, linear CTE
Materials with a low coefficient of thermal expansion maintain
their dimensions more accurately when the temperature changes.

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 Thank you!

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