Materials Science 1:

Atomic Structure
and Interatomic Bonding
Atomic Structure (Chemistry review)
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10-27 kg
• atomic number = # of protons in nucleus of atom
= # of electrons in neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms
1 amu/atom = 1 g/mol
C 12.011
H 1.008 etc.
Prof. Dr.-Ing. John-Glen Swanson 2
Atomic Structure

Some of the following properties

1) Chemical
2) Electrical
3) Thermal
4) Optical
are determined by electronic structure

Prof. Dr.-Ing. John-Glen Swanson 3

Atomic Models
• Bohr atom

• Wave-mechanical model

Prof. Dr.-Ing. John-Glen Swanson 4

Electronic Structure

• Electrons have wavelike and particulate properties.

• Two of the wavelike characteristics are
• electrons are in orbitals defined by a probability.
• each orbital at discrete energy level is determined by quantum numbers.

• Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
 = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (- to +)
ms = spin ½, -½
Prof. Dr.-Ing. John-Glen Swanson 5
Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J. Wulff,
Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

Prof. Dr.-Ing. John-Glen Swanson 1s K-shell n = 1 6

SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 9e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
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)
• Why? Valence (outer) shell usually not filled completely.
Prof. Dr.-Ing. John-Glen Swanson 7
Electron Configurations

• Valence electrons – those in unfilled shells

• Filled shells more stable
• Valence electrons are most available for bonding and tend to control
the chemical properties

• example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

Prof. Dr.-Ing. John-Glen Swanson 8

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d valence
4p N-shell n = 4
electrons
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J.
Wulff, Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
9
Prof. Dr.-Ing. John-Glen Swanson
The Periodic Table
• Columns: Similar Valence Structure

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

accept 2e-
accept 1e-
give up 3e-
H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.8,
Callister &
K Ca Sc Se Br Kr
Rethwisch 9e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons 10
Prof. Dr.-Ing. John-Glen to
Swanson
become + ions. to become - ions.
Electronegativity
• Ranges from 0.9 to 4.1,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

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Prof. Dr.-Ing. John-Glen Swanson
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

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

[Ne] [Ne]

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Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
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Ionic Bonding
• Energy – minimum energy most stable
• Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - + n
r r
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig.
2.10(b), Callister &
Rethwisch 9e.

Attractive energy EA
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Prof. Dr.-Ing. John-Glen Swanson
Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

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Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: H2
H2

Each H: has 1 valence e-,

needs 1 more
H H
Electronegativities
are the same.
shared 1s electron shared 1s electron
from 1st hydrogen from 2nd hydrogen
atom atom

Prof. Dr.-Ing. John-Glen Swanson Fig. 2.12, Callister & Rethwisch 9e.
16
 Bond Hybrization
• Carbon can form sp3 hybrid
orbitals

Fig. 2.14, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4 th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Prof. Dr.-Ing. John-Glen Swanson

Fig. 2.13, Callister & Rethwisch 9e. 17
 Covalent Bonding: Carbon sp3
• Example: CH4

C: has 4 valence e-,

needs 4 more
H: has 1 valence e-,
needs 1 more

Electronegativities of C and H
are comparable so electrons Fig. 2.15, Callister & Rethwisch 9e.
are shared in covalent bonds. (Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4 th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Prof. Dr.-Ing. John-Glen Swanson

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Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

x (100%)
% ionic character =

where XA & XB are Pauling electronegativities

Ex: MgO XMg = 1.3
XO = 3.5

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Secondary Bonding
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.20,
bonding
Callister & Rethwisch 9e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.22,
Callister & Rethwisch 9e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

Prof. Dr.-Ing. John-Glen Swanson
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Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
Prof. Dr.-Ing. John-Glen Swanson
inter-molecular 21
Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”
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Properties From Bonding: α
• Coefficient of thermal expansion, α
length, L o coeff. thermal expansion
unheated, T1
ΔL ΔL
= α (T2 -T1)
heated, T2 Lo

• α ~ symmetric at ro
Energy
unstretched length
ro
r α is larger if Eo is smaller.

E
larger α
Prof. Dr.-Ing. John-GlenoESwanson smaller α 23
Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small α

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large α
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