MS31007: Materials Science

Chapter 2
Atomic Structure and Bonding
-Interatomic Bonding
–Bonding forces and energies
Panoramic view of what materials are
composed of –Primary interatomic bonds
and what holds them together –Secondary bonding
–Molecules

Instructor: Prasana Kumar Sahoo

Material Science Centre
E-mail: [email protected]
 Chapter 2: Atomic Structure and Bonding
Revisiting Concepts – Material Science Context
● Define four quantum numbers for electrons and explain the significance of each.
● Explain the arrangement of the elements in the periodic table.
● State the electronic structure of the elements.
● Explain the role of electronegativity in bonding.

● Define four different mechanisms of bonding in materials.

● Understand how interactions between atoms or between ions influence
materials properties.
● Recognize that even though allotropes are composed of the same
element, they can display dramatically different materials properties
based on their structure (e.g., the allotropes of carbon).
 Electrons in Atoms
The electrons form a cloud around the nucleus, of radius of 0.05 – 2 nm.
Only certain “orbits” or shells of electron probability densities are allowed
The shells are identified by a
principal quantum number n,
which can be related to the
size of the shell, n = 1 is the
smallest;
n = 2, 3 .. are larger.

The second quantum

number l, defines subshells
within each shell.
Two more quantum numbers
characterize states within the
subshells.

Pauli Exclusion Principle:

only one electron can have a given set of the four Quantum numbers
 Quantum Numbers
The quantum numbers arise from solution of
Schrodinger’s equation

Eigenvalues are discrete

energy levels for electron

Square of eigenfunction gives probability density (where

electron can be found)

meZ4

a0= Bohr radius

Comparison of the (a) Bohr and (b) wave mechanical atom
models in terms of electron distribution
 Electrons in Hydrogen Atoms
The Bohr model for an electron transition in H between quantized energy levels with different
quantum numbers n yields a photon by emission with quantum energy:
 Electrons in Hydrogen Atoms

(a) The first three electron energy states for the Bohr hydrogen atom.
(b) Electron energy states for the first three shells of the wave-mechanical hydrogen atom
 Quantum Numbers
In wave mechanics, every electron in an atom is characterized by four parameters called quantum numbers.
The size, shape, and spatial orientation of an electron’s probability density (or orbital) are specified by 4 quantum
numbers, n, l, ml, ms
➢ Principal quantum number (n) = 1, 2, 3, …. ;
➢ Azimuthal or subsidiary quantum number (l) = 0, 1, 2, n-1
➢ Magnetic quantum number (ml )= 0, 1, 2, ±l ;
➢ Electron Spin Quantum Number (ms) = ± ½ called “spin up”
or “spin down”

Sub-energy
levels-subshells

Very minor effect on the energy of an e- Specifies the spatial orientation of the
atomic orbitals and has little effect on
the energy of e-
 Quantum Numbers: Filling of Orbitals
Electrons that occupy the outermost filled shell – the valence electrons – they are responsible for
bonding. Electrons fill quantum levels in order of increasing energy (only n, l make a significant difference).

Argon, Z = 18: 1s2 2s2 2p6 3s2 3p6

Examples:
Iron, Z = 26: 1s2 2s2 2p63s2 3p6 3d6 4s2
Electrons in Atom: Filling of Orbitals
Electron configurations where all
states within valence electron shell
are filled are stable → unreactive
inert or noble gas.
 Periodic Table
Arranged by atomic number, electron configuration & recurring chemical properties
Group 18
 Electrons in Atom: Filling of Orbitals
The periodic table for which the rows of the Lathanoid and Actinoid series
are inserted into their correct positions. The column heading indicates the
particular orbital being filled by each additional electron as the atomic
number increases.
 Electrons in Atom: Physical and Chemical properties

• Ionization energy
is the minimum
amount of energy
required to
remove the
valence electron,
of an isolated
neutral atom or
molecule

• Electron affinity is
defined as the amount
of energy released
when an electron is
attached to a neutral
atom or molecule
 Periodic Table –Atomic Radius

• Atomic radius
increases with
increasing period

• Atomic radius
decreases with
increasing group
 Electronegativity, 
 is a measure of the ability of an atom in a molecule to attract electrons to itself

Concept proposed by
Linus Pauling
1901-1994

The only person to receive two

unshared Nobel prizes
(for Peace and Chemistry).
Chemistry areas: bonding,
electronegativity, protein structure
 Periodic Table

give up 1e-

give up 2e-

Accept 2e-

Accept 1e-

Inert gases
give up 3e-

Electropositive elements: Electronegative elements:

Readily give up electrons to become + ions. Readily acquire electrons to become - ions.
 Periodic Table - Electronegativity

• Electronegativity - a measure of how willing atoms are to accept electrons

• Subshells with one electron → low electronegativity
• Subshells with one missing electron → high electronegativity
• Electronegativity increases from left to right
• Metals are electropositive – they can give up their few valence electrons to become positively charged ions
Periodic Table – Electrical Conductivity
 Endangered Elements and their Conservation
By 2050, the
cumulative
demand for lithium
could reach over 60
million metric tons,
which is more than
ten times the
current annual
production (Roskill,
2020)
How will we save our endangered elements?
Bonding Forces and Energies

Considering the interaction between two

isolated atoms as they are brought into
close proximity from an infinite separation.

Will the atoms collapse on

themselves?
What happens to the atomic electrons when two or more
widely separated atoms are brought together to form a molecule?
 Electrons in Molecule or Solids: Bonding Forces and Energies
Two distant H atoms are brought together to form a H2 molecule: Two cases can happen

• Electron charge
Electron density is enhanced in the density is enhanced on
region between the nuclei: the side of each nucleus
preponderance of negative charge binds away from the other
the positively charged nuclei together; nucleus.
an energy reduction occurs
• Because little negative
charge is left between
Condensation to the solid state the positive nuclei -
There must be a final overall strongly repel each other
reduction in the total energy of individual on approach, and the
energy rises.
atoms when they interact and form stable molecules or solids.
 Example of Bonding: Electron Transfer in Ionic Molecules
An ionization energy of 5.4 eV is required to
remove the electron and create a Li+ ion

Incorporation of an
electron to 2p shell
-leads to an energy
reduction of 3.6 eV.

During electron transfer between these atoms as they draw close, there is actually a surprising increase in energy of
5.4 eV - 3.6 eV = 1.8 eV!
Why do they then react to form molecules?
The answer is that the ions are not as close to each other as they could be.
The potential energy of interaction (U) As r shrinks, a point is reached where
associated with the force between these U= -1.8 eV, and the energy is recovered
point charges is
-leading to the net energy reduction required for bonding
 Nature knows how to strike a compromise
By adding attractive and repulsive components

Equilibrium distance ro = the attractive and repulsive forces

balance; calculated by minimizing U with respect to r.
Simple differentiation

Interaction of Atomic Pairs ?

The huge collection of atoms that condense to form a solid is very
different from an interacting pair of atoms that form a molecule.

In condensed materials with weaker secondary bonds that keep molecules attached to one another (e.g., polymers,
ice, liquid gases), m and n are frequently taken as 6 and 12, respectively
If m = 1 we have the case of the alkali halide solid
Forces between Atoms

• The force-distance (F–r) curve for two

materials, showing the relationship between
atomic bonding and the modulus of elasticity.

Relationship
between atomic
bonding and the dr
dr
modulus of
elasticity

• A steep dF/dr slope gives a high modulus.

 Interatomic force-distance curves: coefficient of thermal expansion (α)
α is the fractional change in linear dimension of a material per degree of temperature
where L is length and T is temperature
α = (1/L)(dL/dT) - related to the asymmetry of the energy-separation curve

Symmetric F-r curve: the thermally induced atomic motion in the Asymmetrical F-r curve: At temperature T1 the average
positive and negative r directions will always average to r = ro, And
as the temperature is raised the amplitude of vibration increases displacement or midpoint between the well walls falls
but the average value of r is still ro . slightly to the right of ro
Hence there is no thermal expansion.
-the material thermally expands
 When atoms come together: Band Structure of Solids?
In forming a solid, N widely - the valence electrons of atoms at distinct energy states get split into closely spaced
spaced atoms in a gas phase electron states and form wide electron energy bands when they form a solid. These
can be imagined bands are separated by gaps, where electrons cannot exist.
to condense according to the
chemical reaction

G and S refer to the

gas and solid atoms

Uo- bonding energy

- magnitude of Uo
is the heat
liberated when
elements react to
form the solid
- sublimation
energy of the
solid
Core-level electron
 Energy Band Structures in Solids
For N atom solid
s band has N states
p band has 3N states
The extend of energy states splitting
depends on inter-atomic distance

Conduction
band

In solids gap between states

valence band
could be 10-10 eV apart

Outermost shells start forming bands

as atoms get closer, however core Valence band – filled – highest
partially or completely occupied
shells may not form bands as still far energy levels
from each other. Conduction band – empty – lowest
unoccupied energy levels
Simple electron model of a metal
Simple electron model of a metal
consisting of individual
unbroadened and broadened
atomic core levels,
surmounted by a distribution of
conduction electrons.
• It is possible to transfer some electrons from metals
into an adjacent vacuum by heating them to a
sufficiently high temperature.
The operation of vacuum tubes, including the TV
picture tube, depends on this thermionic emission
of electrons.

• work function energy (qφ), a kind of electrostatic

barrier that prevents conduction electrons from
leaving the metal
~ (2 - 5 eV)
 Electrons in Metals: Conduction Electrons
The outermost valence electrons of metal atoms are so critical to the bonding, chemical, and electrical properties
of metals as well as semiconductors, they are variably known as valence or conduction electrons.
One may imagine that a well or box of length L with impenetrable walls, encloses this dense collection of electrons (e.g., one per
atom) that are totally delocalized from the atoms.
- assume that these electrons only see a constant electric potential (V), whose magnitude ~ be zero everywhere
- electrons at zero potential are free, and the de Broglie relationship implies ~ waves associated with them
If an electron moving in the x direction is considered, the longest λ it
can have is 2L. Because the electron changes velocity (v) as it
reflects from each wall, all of its possible associated waves have
nodes there. - electrons can never extend past them
➢ represented as sine waves of the form
➢ The kinetic energy of these electrons is given by

nx is an effective quantum number that describes HOME WORK

electron motion or wave propagation in the x direction

(A) An electron particle in a cubic box that has impenetrable walls. (B) Allowed electron
wavefunctions for the particle in the box.
 Electrons in Metals: Core Electrons
Calculated overlapping 3s and 3p energy levels in Na
As the individual metal atoms approach each metal as a function of interatomic separation
other they do not transfer electrons, one to the
other—alkali halide style—because this is not
profitable energetically.

Some new levels are higher than the original

one, elevating the energy and contributing to
antibonding effects; but importantly, new lower
energy levels are produced and they are in the
majority. As a result, atoms are bound together
in the solid because a net energy reduction is
achieved.
1s22s22p63s1
 Band Structure of Sodium
Sodium is a metal and has the electronic structure
Na and other alkali metals in column 1A of
the periodic table have only one electron in
the outermost s level. The 3s valence band in
Na is half filled and, at absolute zero, only the
lowest energy levels are occupied.

The energy levels broaden into bands. The

3s band, which is only half filled with
electrons, is responsible for conduction in Na.
Note that the energy levels of the orbitals in
the 1s, 2s, and 2p levels do not split at the
equilibrium spacing for sodium.
 Band Structure of Diamond
The elements in Group 4—C (diamond), Si, Ge, and tin—contain two electrons in their outer p shell and
have a valence of four. We might expect these elements to have a high conductivity due to the unfilled p
band, but this behavior is not observed!

These elements are covalently bonded; - the electrons in the outer s and p bands are rigidly bound to
the atoms- which produces a complex change in the band structure.

When C atoms are brought together to form

solid diamond, the 2s and 2p levels interact
and produce two bands. Each hybrid band can
contain 4N electrons, Since there are only 4N
electrons available,

• The valence band is completely full

• Conduction band is empty at 0 K
• A large energy gap (Eg, 5.5 eV)

Electrical conductivity of Diamond

is less than 10-18 ohm-1 cm-1
 Formation of energy bands in Silicon
Formation of energy bands in silicon as isolated atoms are brought together
Energy gap (Eg)
Eg =1.12 eV in silicon,
Eg = ~6 eV in C (diamond)
Eg = 0.68 eV in Ge

Au= 4.10 X 107 S/m, Fe=9.93x106 S/m

The admixture or hybridization of the 3s and 3p electrons

leaves an energy gap in the bands at the equilibrium spacing
silicon–silicon bonds (2.358 Å)
 Magnesium metal (Semi-metal)

Mg- 1s22s22p63s2
Mg has this band structure. Each isolated Mg atom has two 3s electrons.
However, when a solid is formed, the 3s and 3p bands overlap.
 Electrical properties are a consequence of the band structure!
• Valence band – filled – highest partially or completely
occupied energy levels
• Conduction band – empty – lowest unoccupied energy levels
• Fermi Energy – highest filled state at 0 K
Conduction
band

valence band

Why does this matter?

Can have empty or Whether or not there is an energy band
partially filled bands gap, and if so, how large it is,
determines the electrical properties of
materials. WHY?
Additional Information
 Nature of Interatomic Bonding
Why the individual atoms coalesce into larger structures and take
on the characteristics and properties of many different materials?
The bonding mechanisms between atoms are closely related to the
structure of the atoms themselves.
Atoms = nucleus (protons and neutrons) + electrons
Charges: Electrons and protons have negative and positive charges of
the same magnitude, 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.

Masses: Protons and Neutrons have the same mass, 1.67 × 10-27 kg.
Mass of an electron is much smaller, 9.11 × 10-31 kg and can be neglected
in calculation of atomic mass.

The atomic mass (A) = mass of Protons + mass of Neutrons

# protons gives chemical identification of the element
# protons = atomic number (Z)
# neutrons defines isotope number
 Atomic mass units. Atomic weight
The atomic mass unit (amu) is often used to express atomic weight.
1 amu is defined as 1/12 of the atomic mass of the most common isotope of carbon atom that has 6
protons (Z=6) and six neutrons (N=6).
Mproton ≈ Mneutron = 1.66 x 10-24 g = 1 amu.
The atomic mass of the 12C atom is 12 amu.
The atomic weight of an element = weighted average of the atomic masses of the atoms naturally occurring
isotopes. Atomic weight of carbon is 12.011 amu. The atomic weight is often specified in mass per mole.

A mole is the amount of matter that has a mass in grams equal to the atomic mass in amu of the atoms
(A mole of carbon has a mass of 12 grams).

The number of atoms in a mole = Avogadro number,

Nav = 6.023 × 1023

1 amu/atom = 1 gram/mol
Example: Atomic weight of iron (Fe) = 55.85 amu/atom
= 55.85 g/mol
 Some simple calculations
The number of atoms per cm3, n, for material of density d (g/cm3) and atomic mass M (g/mol):

n = Nav × d / M
Graphite (carbon): d = 2.3 g/cm3, M = 12 g/mol,
n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol = 11.5 × 1022 atoms/cm3

Diamond (carbon): d = 3.5 g/cm3, M = 12 g/mol

n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol = 17.5 × 1022 atoms/cm3

Water (H2O) d = 1 g/cm3, M = 18 g/mol

n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3

For material with n = 6 × 1022 atoms/cm3 we can calculate

mean distance between atoms L = (1/n)1/3 = 0.25 nm.