ES21B

FUNDAMENTALS OF
MATERIALS
SCIENCE AND
ENGINEERING
 ATOMIC STRUCTURE

2
chapter

AND INTERATOMIC
BONDING
FUNDAMENTALS OF MATERIALS SCIENCE AND ENGINEERING
ATOMIC STRUCTURE

6 26
C Fe
12.01 55.85
BOHR AND WAVE-MECHANICAL ATOMIC MODEL
BOHR AND WAVE-MECHANICAL ATOMIC MODEL
WAVE-MECHANICAL ATOMIC MODEL
•Electrons have wavelike and particulate properties.
• This means that electrons are in orbitals defined by a
probability.
• Each orbital at discrete energy level is determined by
quantum numbers.
QUANTUM NUMBERS
•Using wave mechanics, every electron in an atom is
characterized by four parameters called quantum
numbers
• n, principal quantum number (n=1, 2, 3 or K, L, M)
• l, subsidiary, (s, p, d, f) (0, 1, 2, 3)
• ml, magnetic (s=1, p=3, d=5, f=7) (-l to l)
• ms, spin moment (+½, -½)
RELATIVE ENERGIES OF THE ELECTRONS
FOR THE VARIOUS SHELLS AND SUBSHELLS

• the smaller the principal quantum

number, the lower the energy
level
• within each shell, the energy of a
subshell level increases with the
value of the l quantum number
• there may be overlap in energy of
a state in one shell with states in
an adjacent shell
ELECTRON CONFIGURATION
•The electron configuration or structure of an atom
represents the manner in which these states are
occupied.
• Pauli exclusion principle
• Ground state – state when all the electrons occupy
the lowest possible energies
ELECTRON ENERGY STATES

•Electrons have discrete 4d

4p N-shell n = 4
energy states 3d
• tend to occupy lowest 4s

available energy state.

Energy
3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Adapted from Fig. 2.4, Callister & Rethwisch 8e.
SURVEY OF ELEMENTS
Element Atomic # Electron configuration
•The electron Hydrogen
Helium
1
2
1s 1
1s 2 (stable)
configuration for Lithium
Beryllium
3
4
1s 2 2s 1
1s 2 2s2

most elements is Boron

Carbon
...
5
6
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...
not stable. Neon
Sodium
10
11
1s 2 2s 2 2p 6
1s 2 2s 2 2p 6 3s 1
(stable)

Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)
Adapted from Table 2.2, Callister & Rethwisch 8e.
ELECTRON CONFIGURATION
•Ex: Sodium 1s22s22p63s1
•Valence electrons are those
that occupy the outermost
shell. They are most available
for bonding and tend to
control the chemical
properties.
•Filled shells more stable.
ELECTRONIC CONFIGURATIONS
• ex: Fe - atomic #26 = 1s2 2s2 2p6 3s2 3p6 3d6 4s2 valence electrons
4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Adapted from Fig. 2.4, Callister & Rethwisch 8e.
HYBRIDIZATION
•Under special circumstances, the s and p orbitals
combine to form hybrid spn orbitals
THE PERIODIC TABLE
THE PERIODIC TABLE

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-
H He
Li Be O F Ne
Electropositive Na Mg S Cl Ar Electronegative
elements: K Ca Sc Se Br Kr elements:
Readily give up Rb Sr Y Te I Xe
Readily acquire
Cs Ba Po At Rn
electrons to Fr Ra electrons to
become (+) ions. become (-) ions.
Adapted from Fig. 2.6, Callister & Rethwisch 8e.
TRENDS IN THE PERIODIC TABLE

•First Ionization
Energy – minimum
energy required to
remove the most
weakly bound electron
from an isolated
gaseous atom.
TRENDS IN THE PERIODIC TABLE

•Electron
Affinity – energy
change associated
with an isolated
gaseous atom
accepting one
electron.
TRENDS IN THE PERIODIC TABLE

•Atomic Radius –
distance between the
surrounding electron and
the nucleus.
TRENDS IN THE PERIODIC TABLE
• Electronegativity – measure of an attraction an atom
has for electrons in a bond formed with another atom.
Ranges from 0.7 to 4.0.
Larger
Smaller
electro-
electro-
negativity
negativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
ELECTRONEGATIVITY
•As developed by Milliken, it is the average of the
ionization energy and the electron affinity.
𝐼𝐸 + 𝐸𝐴
𝜒=
2
•Widely used is the one developed by Linus Pauling
0.31(𝑛 + 1 ± 𝑐)
𝜒= + 0.5
𝑟
TYPES OF BONDS
• Electronegativity dictates how bonds are categorized, by
providing a measure of the excess binding energies between
atoms A and B.
∆𝐴−𝐵 = 96.5 𝜒𝐴 − 𝜒𝐵 2
• Excess binding energy is related to a measurable quantity,
the bond dissociation energy between two atoms.
1
∆𝐴−𝐵 = 𝐷𝐸𝐴𝐵 − 𝐷𝐸𝐴𝐴 𝐷𝐸𝐵𝐵 2
• The greater the electronegativity difference, the greater the
binding energy.
PRIMARY BONDS
•Created when there is a direct interaction of
electrons between two or more atoms.
•The more electrons per atom involved in the
process, the higher the bond order.
PRIMARY BONDS (4 GENERAL CATEGORIES)
1. Ionic – occurs when electronegativity difference
between two atoms is greater than 2.0.
2. Covalent – occurs when electronegativity difference
between two atoms is less than 0.4.
3. Polar Covalent – occurs when electronegativity
difference between two atoms is between 0.4 and 2.0.
−0.25 𝜒𝐴 −𝜒𝐵 2
%ionic character = 100% × 1 − 𝑒
4. Metallic – electrons are decentralized and are shared by
the core of positive nuclei.
% IONIC CHARACTER
•Example:
Solve for the %ionic character of MgO
 −0.25 𝜒𝐴 −𝜒𝐵 2
%ionic character = 100% × 1 − 𝑒
% IONIC CHARACTER
•Example:
Solve for the %ionic character of MgO
−0.25 𝜒𝐴 −𝜒𝐵 2
%IC = 100% × 1 − 𝑒
−0.25 3.44−1.31 2
= 100% × 1 − 𝑒
−0.25 2.13 2
= 100% × 1 − 𝑒
= 100% × 1 − 2.718282−1.134225
= 100% × 1 − 0.321671
= 67.83% ionic
SECONDARY BONDS
•Secondary or physical forces and energies are also
found in many solid materials
•They are weaker than the primary ones but
nonetheless influence the physical properties of
some materials
HOW DO BONDS FORM?
•Atoms approach each other only at
a certain distance.
•If a bond is formed, they maintain an
equilibrium separation distance
(bond length).
BOND FORMATION
FACTORS AFFECTING BOND FORMATION
1. Attractive Energy
2. Repulsive Energy

•Total potential energy of the system due to bond

formation:
BOND FORMATION
BOND FORMATION
•Bond length, r
r

•Bond energy, E0 Energy

ro (Un-stretched length)
r
E0 = “bond energy”
PROPERTIES FROM BONDING
•Melting Temperature, Tm
Energy

ro
r Tm is larger if E0 is larger.
smaller Tm

larger Tm
PROPERTIES FROM BONDING: a
•Coefficient of thermal expansion, a
length, L o
Energy
unheated, T1
DL unstretched length
r o
heated, T2 r
larger a
-Eo
coeff. thermal expansion -Eo smaller a
DL
Lo
= a (T2 -T1) a is larger if Eo is smaller.
IONIC, COVALENT,
AND METALLIC
PRIMARY BONDS
1. THE IONIC
BOND
PRIMARY BONDS
THE IONIC BOND
•Metal + Nonmetal
donates accepts
electrons electrons
•Dissimilar electronegativities
THE IONIC BOND
•Occurs between + and - ions.
•Requires electron transfer.
•Large difference in electronegativity required.
Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
THE IONIC BOND
•ex: MgO
Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4
[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]
IONIC BONDING IN SODIUM CHLORIDE
THE IONIC BOND
•Aside from the attractive and repulsive energies
due to the bonding of two atoms, an additional
energy due to the transfer of electrons is essential
to describe the energy due to the formation of the
ionic bond.
THE IONIC BOND
•∆Eions is the difference in energy required to form a
cation and an anion.
•∆Eions = IEcation - EAanion
•Example:
Calculate the ∆Eions of NaCl
∆Eions = IEcation - EAanion
THE IONIC BOND
•Example:
Calculate the ∆Eions of NaCl
∆Eions = IENa - EACl
= 498 kJ/mol – 356.1 kJ/mol
= 141.9 kJ/mol
THE IONIC BOND
•Attractive force is given by Coulomb’s Law.
ATTRACTIVE AND REPULSIVE FORCES
•Example: The atomic radii of K+ and Br - ions are
0.138 nm and 0.196 nm, respectively.
• Calculate the force of attraction between these two
ions at their equilibrium interionic separation (i.e.,
when the ions just touch one another).
• What is the force of repulsion at this same separation
distance?
ATTRACTIVE AND REPULSIVE FORCES
•Example: The atomic radii of K+ and Br - ions are
0.138 nm and 0.196 nm, respectively.
𝑍1 𝑒 × 𝑍2 𝑒 (+1)𝑒 × (−1)𝑒
𝐹𝐴 = 2
=
4𝜋𝜀0 𝑟 4𝜋𝜀0 (0.138 × 10−9 + 0.196𝑥10−9 )2
1.602 × 10−19 2
=
4𝜋(8.8541878176 × 10−12 )(0.334𝑥10−9 )2
= 2.07 × 10−9 𝑁
𝐹𝑅 = −𝐹𝐴 = −2.07 × 10−9 𝑁
THE IONIC BOND
•From the attractive force, the attractive energy can
be obtained.

•Using the general expression for potential energy

derived earlier, the repulsive energy can be
obtained.
THE IONIC BOND
•Summing up the corresponding expressions and
simplifying

•In an ordered assembly of atoms called a lattice,

interactions with adjacent atoms must be taken
into account.
EXAMPLES: IONIC BONDING
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
2. THE COVALENT
BOND
PRIMARY BONDS
THE COVALENT BOND
•Molecular Orbital Theory is
used to represent the
bonding.
THE COVALENT BOND
•As long as the number of
bonding electrons is greater
than the antibonding
electrons, the molecule is
stable.
•Electron filling of orbitals
follows Hund’s rule.
THE COVALENT BOND
•For heteronuclear diatomic
molecules, the more
electronegative atom will have
lower molecular orbital
energy.
MOLECULAR ORBITAL THEORY
HYBRIDIZATION
•Mixing of atomic orbitals to
create new orbitals that have
geometries better suited to a
particular type of bonding
environment.
COMMON HYBRIDIZED ORBITALS
•sp3 – has ¼ s and ¾ p characteristic;
results in tetrahedral molecular
structures
•sp2 – has 1/3 s and 2/3 p characteristic;
results in trigonal planar molecular
structures
•sp – has ½ s and ½ p characteristic;
results in linear molecular structures
COVALENT BONDING
•Atoms have similar electronegativity, therefore they
share electrons
•Bonds determined by valence – s & p orbitals
dominate bonding
COVALENT BONDING
•Example: CH4 shared electrons
H
from carbon atom
CH 4
C: has 4 valence e-,
needs 4 more H C H
H: has 1 valence e-,
needs 1 more shared electrons
from hydrogen
Electronegativities H
atoms
are comparable.
Adapted from Fig. 2.10, Callister & Rethwisch 8e.
3. THE METALLIC
BOND
PRIMARY BONDS
METALLIC BOND
•Valence electrons are not bound to any particular
atom in the solid and are more or less free to drift
throughout the entire metal
THE METALLIC BOND
•Consequence of coming together of a large group
of atoms and sharing of valence electrons.
•N atomic orbitals will be formed with the same
(degenerate) energy.
•Bonds are nondirectional.
PARTS OF AN ENERGY BAND
•Core Band – electrons not
involved in bonding
•Valence Band – electrons that
form the electron gas
•Conduction Band – remaining
incompletely filled higher atomic
orbitals
VAN DER WAALS,
DIPOLE-DIPOLE, AND
HYDROGEN BONDING
SECONDARY BOND
SECONDARY BONDS
•Occur due to indirect interaction of electrons in
adjacent atoms or molecules.
SECONDARY BONDS (3 MAIN TYPES)
1. van der Waals Forces – momentary electric dipoles
that can occur in all atoms and molecules due to
statistical variations in the charge density.
2. Dipole-Dipole Interactions – found in molecules that
possesses permanent charge separation or dipoles.
3. Hydrogen Bonding – special type of dipole-dipole
interactions; occurs when hydrogen in a highly polar
molecule gets attracted to a very electronegative atom in
another polar molecule.
SECONDARY BONDING:VAN DER WAALS
•Arises from interaction between dipoles
•Fluctuating dipoles
asymmetric electron ex: liquid H2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

Adapted from Fig. 2.13, Callister & Rethwisch 8e.

SECONDARY BONDING: DIPOLE-DIPOLE
•Permanent dipoles-molecule induced
secondary
general case: + - bonding
+ -
secondary
ex: liquid HCl H Cl bonding H Cl

ex: polymer secondary bonding

Adapted from Fig. 2.15, Callister & Rethwisch 8e.

SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large Nondirectional (ceramics)
Covalent Variable Directional
large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)
Metallic Variable Nondirectional (metals)
large-Tungsten
small-Mercury
Secondary smallest Directional, inter-chain
(polymer), inter-molecular
SUMMARY
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm, large E, small a

Metals Variable bond energy

(Metallic bonding): moderate Tm, moderate E, moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm, small E, large a
THANK YOU FOR
LISTENING! :)
SEE YOU NEXT MEETING