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MS 211
Introduction to Materials Science and Engineering

Atomic Bonding

Dong-Hwa Seo

Department of Materials Science and Engineering

Korea Advanced Institute of Science and Technology (KAIST)
How would you classify materials? How would you describe each group?
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1. Atomic Structure
This model is not to scale.
In reality, atom is mostly
empty space.
Schematic of the model of a 12C atom.
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• Atom is composed of electrons, protons and neutrons.
• Electron is negatively charged. Proton is positively
charged. Neutron has no charge.
• Nucleus is composed of protons and neutrons.
• Planetary model describes an atom by representing it
similarly to our solar system.
-nucleus represented as the sun
-electrons represented as the planets
orbiting around the sun
• However, the electrons DO NOT orbit around the nucleus
as the planets orbit around the sun.
• Electrons behave both as a particle and a wave. Hence,
you can not simultaneously determine its position and
momentum. This concept will be covered in detail when
you take quantum mechanics.
1. Atomic Structure
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• In reality, atoms are mostly empty space.

This model is not to scale.
Hydrogen Nucleus Diameter: ~10-15 m
Hydrogen Atom Diameter: ~10-10 m

Pea: Nucleus
Soccer Stadium: Atom

Schematic of the model of a 12C atom.

Atomic Mass Unit
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What is the mass of atom(s)?

• Each proton or neutron has a mass of 1.66 x 10-24 g
• Electrons weigh 0.911 x 10-27 g about 103 times smaller than protons or
neutrons. Therefore, they are ignored in mass calculation.
• 1.66 x 10-24 g = 1 atomic mass unit (amu)
Question) What is the mass of a Carbon atom in units of amu?
Carbon atoms have an atomic mass of 12.01. Therefore, its mass is 12.01
amu. (98.9% 12C and 1.1% 13C)

• Atomic mass represents the mass of the element in amu units.

Periodic Table
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Atomic Number: Number of Protons

Atomic Mass:
Neutrons+Protons
Avogadro’s Number
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• How do we calculate the number of protons (or neutrons) in 1 gram?

1 𝑝𝑟𝑜𝑡𝑜𝑛 "$ 𝑝𝑟𝑜𝑡𝑜𝑛𝑠
1𝑔× = 6.02×10
1.66×10!"#𝑔
• 6.02 x 1023 is known as the Avogadro’s Number.
• Avogadro’s number is expressed as mole(s).
6.02 x 1023 = 1 mole
ex) 6.02 x 1023 carbon atoms = 1 mole of carbon atoms.
ex) 6.02 x 1023 NaCl compounds = 1 mole of NaCl compounds

Question) If you have 1 mole of carbon atoms, how much does it weigh in grams?

6.02×10"$ 𝑎𝑡𝑜𝑚𝑠 12.01 𝑎𝑚𝑢 (1.66×10!"#𝑔)

1 𝑚𝑜𝑙𝑒 × × × = 12.01𝑔
1 𝑚𝑜𝑙𝑒 1 𝑎𝑡𝑜𝑚 1 𝑎𝑚𝑢

12.01 𝑔𝑟𝑎𝑚𝑠
1 𝑚𝑜𝑙𝑒
Atomic Mass Unit and Avogadro’s Number
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Atomic Mass represents

• Mass of the element

in amu units.
• The mass of the
element in grams per
mole.
Atomic Structure (Review from high school chemistry)
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More loosely
bound

valence electrons

Energy States ard Forbidden

You will learn why in

More tightly quantum mechanics
bound

• Electrons dominantly reside in their orbitals.
• Each orbital has a particular energy level.
• Between the energy levels, there can not be any
energy states.
Every electron has a unique set of quantum numbers
n = Principle Quantum Number
l = Angular Momentum Quantum Number
ml = Magnetic Quantum Number
ms = Spin Quantum Number
 Atomic Orbitals (Review from high school chemistry)
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Angular quantum number

Principle quantum number
Hund’s Rule: How are the electrons in a given atom occupied in the atomic orbitals?
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every orbital in a subshell is singly occupied with one

electron before any one orbital is doubly occupied, and all
electrons in singly occupied orbitals have the same spin.

Note that s and p orbitals can be hybridized: example: carbon and oxygen
Carbon Bonding
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• Carbon has an atomic number of 6

• It therefore has 6 protons
• It therefore has 6 electrons

In carbon, these orbitals hybridize!

ex) sp3 hybridization

2s 2px 2py 2pz 2s 2p 2p 2p

sp3 hybridization sp2 hybridization sp hybridization

sp3 sp3 sp3 sp3 sp2 sp2 sp2 2p sp1 sp1 2p 2p

ex) Diamond ex) Graphite ex) Ethyne

Carbon Bonding
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sp3
2s 2py 2px 2pz

sp2 2s 2py 2px 2pz

sp1 2s 2py 2px 2pz

 Ionic Bonding
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Na Na+
• Result of electron transfer from one
atom to another.
• NaCl: Na transfers electron to Cl so
that both can have a full outer
orbital shell.
• Na becomes Na+ and Cl becomes Cl- .
• Na+ and Cl- are called ions. Positively
charged ions are cations and
negatively charged ions are anions.
• Ionic bonding is a result of
coulombic attraction between
oppositely charged ions.
• Ionic bonds are non directional. Cl Cl-
Ionic Bonding
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Coulombic force of attraction between oppositely charged Note that Cl is bigger than Na
ions is
"
𝐹! = − #!; where 𝐾 = 𝑘$ (𝑍% 𝑞)(𝑍& 𝑞)
a: separation distance between the centers of the ions.
Z: valence of the charged ion (Na+ = +1 and Cl- = -1)
q: charge of a single electron. (1.6 x 10-19 C)
ko="#$! : proportionality constant (9 x 109 Vm/C)
!

Note that by convention, attractive force is positive and

repulsive force is negative.

Coulomic Attraction:
The force of attraction between oppositely
charged species is directly proportional to
the inverse of the distance between the
charges, squared.
Ionic Bonding
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Repulsive force FR exists between two atoms, and is due to the

1) overlapping of similarly charged (negative) electric fields from each
ion.
2) Overlapping of two positively charged nucleus.

𝐹! = 𝜆𝑒 "#/%
𝝀 and r are experimentally determined constants for a given ion pair. r
is typically 8.

Bonding force is the net force between coulombic force of attraction

and repulsive force.

F = Fc+FR (Fc is positive and FR is negative)

Equilibrium bond length (ao) occurs when bonding force is
zero or when Fc = FR
As the two ions get close (< ao)FR dominates.
As the two ions get further apart (> ao)Fc dominates.
Ionic Bonding
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• Bonding energy E is related to bonding

force through the expression
𝑑𝐸
𝐹=
𝑑𝑎
3!
Attractive
Bonding force 𝐸 𝑎1 − 𝐸 𝑎2 = ; 𝐹𝑑𝑎
curve 2
Repulsive • a1 is an arbitrary distance between the
ions.
• When the ions are very far apart, the
Repulsive
Bonding energy bonding energy is zero. Therefore,
curve 3! 2
Attractive
𝐸 𝑎1 = ; 𝐹𝑑𝑎 = − ; 𝐹𝑑𝑎
2 3!
Notice here that when F is positive, E is negative. Meaning
that attractive bond energy is negative by convention.
Ionic Bonding
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• At equilibrium bond length (ao)

F=0, Fc = FR

3"
𝐸 𝑎4 = ; 𝐹𝑑𝑎
Attractive
Bonding force 2
curve
Repulsive

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• At ao the bondenergy is a minimum ( 53 = 0)
Repulsive
Bonding energy
• This is where the bond is the most
curve energetically stable.
Attractive
• Therefore, the bond will maintain the bond
length of ao.
Trough indicates the strength
of the chemical bond
Ionic Bonding
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• Equilibrium bond length can

Planetary
model be written as the sum of two
ionic radii.
Graphical explanation that
shows nucleus and electrons • For NaCl,
ao = rNa+ + rCl-
Hard Sphere • Because bond length is well
Model
defined and is generally the
Show the position of atom. same in all orientations, we
Mainly used due to its simplicity.
can use hard sphere model to
describe atoms.
Soft Sphere • In actuality, electron clouds of
Model
each atom or ion overlap, as
A more precise model
in soft sphere model.
Ionic Bonding in crystal structure
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• NaCl crystal is organized such

that Na+ and Cl- ions are stacked
systematically to maximize the Coulombic
Repulsion
number of oppositely charged
ions adjacent to any given ion. Coulombic
Attraction
• This maximizes coulombic
attraction between Na+/Cl- and
minimizes coulombic repulsion
between Na+/Na+ or Cl-/Cl-

Note that Coulombic Repulsion is due to repulsion between ions of similar charges. (e.g. Cl- and Cl-)
This is different from Repulsive Force, which is due to repulsion between electric fields and nucleus.
Coordination Number
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• Coordination number (CN) is the highest number of adjacent ions or atoms surrounding a reference atom or ion.
• For NaCl, CN is 6. Each ion has 6 nearest neighbors.

Na+
Cl-
Coordination Number
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• Coordination number (CN) is the highest number of adjacent ions or atoms surrounding a reference atom or ion.
• For NaCl, CN is 6. Each ion has 6 nearest neighbors.
• CN can be calculated by considering the greatest number of larger ions that can contact the smaller ion.
• CN is highly dependent on the radius ratio of the two atoms or ions.
• Consider r/R = 0.2 (r: radius of smaller atom or ion and R:radius of bigger atom or ion)

Atoms will generally try to maximize their nearest neighboring atoms BUT not at the expense of lowering
their equilibrium distance.
Coordination Number
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• Minimum r/R for CN = 3 is 0.155.

Coordination Radius Ratio, Coordination
Number r/R Geometry

0.225

0.225
Example Problem
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Calculate the minimum radius ratio for a coordination number of 8.

2𝑅 + 2𝑟 = 3𝑙
2𝑅 = 𝑙
𝑙
2𝑅 + 2𝑟 = 2𝑅 3
3𝑙
2𝑟 = 2𝑅 3 − 1
!
= 3 − 1 = 0.732
2𝑙 "
Example Question
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Estimate the coordination number for each of the these ceramic oxides: Coordination Radius Ratio,
Al2O3, B2O3, CaO, MgO, SiO2, and TiO2 Number r/R

Ion Type Radius (nm)

Oxide r/R CN
Al (3+) 0.057
Al2O3 0.057/0.132=0.43 6
B (3+) 0.02
B2O3 0.02/0.132=0.15 2
Ca (2+) 0.106
CaO 0.106/0.132=0.8 8
Mg (2+) 0.078
MgO 0.078/0.132=0.59 6
Si (4+) 0.039
SiO2 0.039/0.132=0.3 4
Ti (4+) 0.064
TiO2 0.064/0.132=0.48 6
O (1- or 2-) 0.132
Covalent Bonding
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• Covalent bonding shares valence electrons between two

Shared
adjacent atoms.
Electrons
• Valence electrons are outer orbital electrons that take part in
bonding.
• Covalent bonding is highly directional.
• Cl for example forms covalent bonding with itself.
Cl: 1s2 2s22p6 3s23p5
Valence
Shared Electrons
Electrons
Valence Valence
Electrons Electrons

Cl Cl
Covalent Bonding
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Example (Fig. 2.13): Cl2 gas Cl: 1s2 2s22p6 3s23p5

Two electrons are shared between two Cl atoms. Shared electrons

Planetary model Electron-dot schematic

Electron density Bond-line schematic

Electron density increased.

But these configurations do not provide the details of covalent bonding.
Covalent Bonding
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Cl: 1s2 2s22p6 3s23p5

Covalent Bonding
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• Diamond is sp3 hybridized carbons linked together • Graphene is sp2 hybridized carbons linked together
• It is 3-dimensional by nature. • It is 2-dimensional by nature.

Valence Electrons Valence Electrons

sp3 sp3 sp3 sp3 sp2 sp2 sp2 2p

Covalent Bonding
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Valence Electrons Valence Electrons

sp3 sp3 sp3 sp3 sp2 sp2 sp2 2p

Polyethylene
Covalent Bonding
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• Covalent bonding can produce coordination numbers

substantially smaller what is predicted by r/R ratio.
• For example, diamond has r/R=1, so it should have CN of
12. But it only has 4.
• CN is determined by the nature of sp3 hybridization
bonding.

• In some cases, CN can be predicted based on r/R ratio.

• For example, even though SiO44- is formed via covalent
bonding, its CN is in agreement with r/R ratio.
!!"#$ "."$% &'
= = 0.295
!%&' ".($) &'
• Si-O bonding has both ionic and covalent character.
Covalent Bonding
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• Bonding force and bonding energy curves for covalent bonding look similar to that of ionic bonding.
• The ionic force equations do not apply in covalent bonding.
• General terminology of bond energy and bond length apply in both ionic and covalent bonding.
Metallic Bond
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• Ionic bonds transfer electrons from one atom to another and is non-directional.
• Covalent bonds share electrons between atoms and is directional.
• Metallic bonds share electrons between many atoms and is non-directional.
• As with ionic bonding, metallic bonding angles and CN can be predicted by r/R ratio
• Electrons are delocalized in metals. They are not bound to individual atoms but are spread throughout the entire
solid.

Electron cloud from

valence electrons

Cu2+ ion core

(cutaway view)

• Metals have high electrical and thermal

conductivity because of the delocalized
electrons.
Metallic Bond (Heat of sublimation)
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Heats of Sublimation (at 25°C) of Some Metals and Their Oxides

Heat of sublimation Heat of sublimation
Metal
• In metal, it is more useful to Metal kcal/mol kJ/mol Oxide kcal/mol kJ/mol
represent the energetics associated Al 78 326
with the bulk solid rather than
isolated atoms (or ions) pairs Cu 81 338
• Heat of sublimation is the amount Fe 100 416 FeO 122 509
of thermal energy needed to turn 1
mol of solid to vapor at given Mg 35 148 MgO 145 605
temperature and pressure. Ti 113 473 α -TiO 143 597
TiO2 153 639
(rutile)
Source: Data from JANAF Thermochemical Tables, 2nd ed., National Standard Reference Data Series, Nat. Bur.
Std. (US)37, (1971), and Supplement in J. Phys. Chem. Ref. Data, 4(1), 1–175 (1975).
Primary Bonds
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Ionic Covalent Metallic

• Non-directional • Directional bonds • Adjacent atoms
bonds • Electron sharing share electrons in
• Electron transfer between adjacent a non-directional
from one atom to atoms way.
another • Electrons are
• Forms a + cation delocalized
and a – anion throughout the
solid

These are all classified as “Primary Bonds.”

Secondary Bonds (van der Waals bonds)
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• Secondary bonding are bonding without electron transfer or sharing.

• Argon has a completely filled orbital so they do not undergo primary bonding.
• However, when two Ar atoms come close to each other, negative charge is drawn slightly towards the
positive nucleus of the adjacent atom. This is known as “induced dipole.”
• Bond energy is very small: ~1 kJ/mol. Note that primary bond energy is ~200-700 kJ/mol
Secondary Bonds
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• Secondary bonding involving permanent dipole is stronger than that of

induced dipole.
• Because oxygen is more
electronegative than hydrogen, water
Hydrogen Bonding molecule tends to be polar.
• Oxygen of one water molecule and
Hydrogen of another molecule form a
bonding. This is an example of
permanent dipole.
• Bond energy is around 21 kJ/mol.

Liquid Water Ice

Covalent Bonding
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Polyethylene Polymer (low strength and low Tg ~ 120 ˚C) Diamond (High strength and high Tm ~ 3500 ˚C)

Diamond has a much higher strength and melting temperature. Why?

Summary of Different bonds and Melting Points
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Summary of Different bonds and Melting Points
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Sodium chloride (table High melting point and high

salt) is an example of ionic strength
bonding

Carbon (diamond) has high

melting point and strong
covalent bond
Modestly strong bonding
because of permanent
dipole

Pure example of secondary Polymer with weaker bonds

bonding has a low softening point
Summary of Different bonds and Melting Points
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(For Silicon)