GE 201/203

Introduction to Materials Science and

Engineering
Lecture 3: Atomic Structure and Interatomic Bonding
07/08/2019
Atomic Structure and Interatomic Bonding
 Atomic structure
 Electron configurations in atoms
 The periodic table
 Various types of primary and secondary interactions
that holds together the atoms that compose a solid.

2
Atomic Models
Dalton: “Billiard Ball” Model
Indivisible unit of an element: atom
Thomson: “Plum Pudding” Model
Discovers electrons, believed to reside
within a sphere of uniform positive charge
Rutherford:
Demonstrates the existence of a positive charged nucleus
that contains nearly all the mass of an atom

Bohr:
Proposes a fixed circular orbits around the nucleus for electrons

Schrodinger: “Electron Cloud” Model / Wave-Mechanical Model

Electrons occupy regions of space (orbitals) around the nucleus
Determined by their energies

*https://www.pinterest.com/madisonkaminsky/daltons-atomic-model/ 3
Atomic Structure – Bohr Atomic Model (1911)
Dense nucleus of protons and neutrons.
n: principle Z: number of protons, N: number of neutrons
quantum
number Electrons “orbit” the nucleus within discrete shells associated
with discrete energy values.
n=3
Valence Electrons
n=2 Electrons furthest from the nucleus.
Extremely important for bonding, conduction of heat
n=1 +12 and electricity, etc.

Atomic Number
= Number of protons (1 for Hydrogen, 94 for Plutonium)
= Number of electrons (for neutral atom)

Atomic Mass (A) ≈ Z+N

This model will work pretty well for this class most of the time,
but remember:
The actual “shape” of atoms depends on the specific electron
Bohr Model orbitals involved, especially the outermost orbitals.

Example: Magnesium
 The Periodic Table inert gas
+1
Valence
+2 -2 -1
electrons

Electronegativity
increases
Electropositive elements: Electronegative elements:
Readily give up electrons to become + ions. Readily acquire electrons to become – ions.

5
 Interatomic Interactions

Repulsive energy
Attractive energy
Bond length

FN = FA+ FR
FN = 0 (@ equilibrium)
Bond energy

The magnitude of E0 & the shape of the energy-interatomic

separation curve vary from material to material,
& both depend on the type of atomic bonding.
6
Bonding → Properties
Callister WD, Retwisch DG, “Fundamentals of Materials Science and Engineering”, 2011, 9th Ed. (Figure 2.10)
Primary Bond Details
Consider bringing two atoms that will bond toward each other from infinite separation.
When the atoms are far apart, a dominant attractive force acts
on them. The exact dependence of Fa on r depends on the type
of bonding.
As the atoms approach one another, the attractive force
increases. Eventually the overlapping of electron orbitals
produces a repulsive force that increases in magnitude
as the atoms are brought closer and closer.
Since these forces oppose one another and are mathematically
distinct, a unique separation exists for which the net force
between the atoms is zero. This distance, ro , is the equilibrium
separation for two isolated atoms.
A force as a function of separation distance can be integrated
to give a potential energy. In this perspective, a unique
separation distance exists for which the energy of the system
is minimized.
A qualitative understanding of these curves is important
for understanding many concepts throughout this course. 7
 Interatomic Interactions (cont’d)
The magnitude of E0 & the shape of the energy-interatomic separation curve
vary from material to material, & both depend on the type of atomic bonding.
Bonding → Properties

Material Properties that are affected by Bonding are:

Bond length

Melting point (Tm)

State (gas, liquid, solid)

Elastic Modulus (E) Thermal Expansion Coefficient (α)

Bond energy

8
Callister WD, Retwisch DG, “Fundamentals of Materials Science and Engineering”, 2011, 9th Ed. (Figure 2.10)
Atomic Bonding in Solids

9
 Atoms want an octet of valence electrons like
Atoms like to bond. the noble gases, which are fairly inert. They
have a stable electron configuration so they
rarely participate in reactions.

+11
Metals will tend to donate electrons to non-
+17
metals during reactions.

+11 +17

1+ 1- 10
 Atoms want an octet of valence electrons like
Atoms like to bond. the noble gases, which are fairly inert. They
have a stable electron configuration so they
rarely participate in reactions.

+11
Metals will tend to donate electrons to non-
+17
metals during reactions.

Na+ and Cl- ions

bond in an orderly,
periodic fashion
to form a solid
NaCl crystal.

+11 +17 After the electron is

transferred, an
attractive force exists
between the
oppositely charged Sodium Chloride: NaCl
ions.
1+ 1- 11
Bonding – Primary Bonds
It’s all about the electrons. Ionic
e- transfer
Metals give electrons to non-metals, resulting in
ions.

Force arises between oppositely charged ions.

Covalent
e- sharing
Close proximity results in orbital overlap.
Favorable for electrons to reside within
the overlap, thus binding the atoms.

Metallic
e- “municipool"
Valence electrons are donated to the bulk
material and are free to move / conduct.
12
Metallic Bonding Analogy
Positive atom cores (blueberries) suspended in a continuous volume of negative charge (jello).

The abundance of free electrons in metals provides:

High electrical and thermal conductivities.

Metals accommodate structural defects

and mechanical strain much better
than covalent & ionic systems.

13
Types of Bonds
 Primary Bonding (Chemical)

 Ionic (transfer of valence electrons)

 Covalent (sharing valence electrons, directional)

 Metallic (delocalization of valence electrons)

 Secondary or van der Waals Bonding (Physical)

 Dipole – Dipole

 H-bonding

 Fluctuating Induced Dipole Bonds

 Polar Molecule-Induced Dipole Bonds

14
Secondary Bonding – van der Waals Bonds
 weaker bonds comparing to primary or chemical bonds
 exist between virtually all atoms and molecules
 arise from atomic or molecular dipoles, coulombic interactions between + & -.
Fluctuting Induced Dipole (H2, Cl2)
Permanent Dipole
Polar Molecule-Induced Dipole (HCl)

H-bond
Special case of vdW
H-N, H-O, H-F

Textbook, Figure 2.20, 2.21 and 2.22. 15

Bonding
Generally
Increasing
Bond Strength
Primary / Chemical
Strong Bond strength is
somewhat
correlated with the
melting temp.

Secondary /
Van der Waals
Weak

16
Bonding – The Big Picture
Generally Increasing Bond Strength

Metallic Covalent Ionic

spheres are atoms spheres are ions
spheres are atoms

C (Graphite) C (Diamond)
Al, Cu, Ag, Au … Silicon NaCl, KCl, FeO
Strong covalent bonding within graphite
sheets. Weaker secondary bonding
between sheets.

C-H and O-H bonds within CH4 and H2O molecules are covalent.
Fe, Na, W …
Bonding between these molecules would be vdW (secondary) CsCl
17
bonds, such as in solid methane and ice.
Bonding – Directionality and Constraints
Generally Increasing Geometric Requirements / Constraints

Metallic Covalent Ionic

Non-directional attraction
promotes ductility and high density.
Directionally-dependent attraction
dictated by orbital shape promotes
lower ductility and lower density.
Non-directional bonds.
A charge registry in the solid-state
hinders displacement / shifting of
ions to arbitrary positions, severely
limiting ductility.

Al, Cu, Ag, Au … C (Graphite)

NaCl, FeO, …

Fe, Na, W … C (Diamond) 18

Silicon CsCl
 Mixed Bonding
A bond can have mixed character depending on the difference in electronegativity between atoms of
interest.

Sn, Si, Bi, etc.

Cu, Ag, Fe

CuZr, CuZr2
Al2O3, TiN

We’re not talking about the simultaneous presence of multiple, “pure”, bonding schemes here.
We’re talking about a particular bond having characteristics of multiple bond types, such as partly covalent & partly ionic.
There is a continuum between the extreme bond types. 19
Bonding – Summary
Type Bond Energy Comments

Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular
Adapted from Dr. Mert Efe & Dr. Arcan Dericioğlu’s slides. 20