Engineering Materials

MEEN 225

Prof. Polychronopoulou kyriaki

Lecture 3
Atomic Structure & Interatomic
Bonding

• What promotes bonding?

(driving
• What force)
types of bonds are there?

• What properties are inferred from

bonding?

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Atomic Structure (CHEM 115!!)

• atom – electrons – 9.11 x 10-31 kg

protons
neutrons
}1.67 x 10-27 kg

• atomic number (Z) = # of protons in nucleus of atom

= # of electrons of neutral species

• Atomic mass (A): sum of mass of neutrons & protons

• Atomic mass unit = amu = 1/12 mass of 12C

Atomic weight = mass of 6.022 x 1023 molecules or atoms

1 amu/atom ==> 1g/mol

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Atomic Structure

• Valence electrons determine all of the following

properties

1) Chemical
2) Electrical
3) Thermal
4) Optical

4
 Electrons in atoms

Bohr’s model (simplified)

(Rutherford-Bohr Model (1931)

1. Discrete orbits (position of http://

electrons well defined) www.beta.facebook.com/

people/Niel-Bohr/
Electron=particle 100002165325948

2. Electron energy is quantized

(specific values). Electron may
take or emit energy.

Quantum mechanics: set of

rules for atomic and subatomic
behavior (Position and Energy)

P5
Wave-mechanics model
1.Electron:
Electronswave-like
have wave + and particle
particle-
form Wave mechanical model

2. Electron has various positions

like
around nucleus
Heisenberg
3. Position is defined by a
probability curve
uncertainty

principle

Bohr’s model

Position of electron is described by a probability distribution

(cloud)
P6
 probability amplitude Ψ with time.

Schrödinger equation:

is a partial differential equation that describes how the quantum state of some physical

system changes with time.

It was formulated in late 1925, and published in 1926, by the Austrian physicist Erwin

Schrödinger.
Electronic Structure
• wave-like and particle properties.
–electrons are in orbitals defined by a probability.
–Each orbital discrete energy level is determined
by quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3,
etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,
…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

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ybridization: merging of different orbital
Nodes

and lobes

P9
 Bohr vs. wave-mechanical
1. Probability to define e-
position

Energy states-
2. Electron energy is quantized
Shells
into shells and subshells

+Subshells (are
governed by
Q.N)
are introduced
in model (b) Bohr hydrogen atom Wave mechanics
hydrogen atom

P10
Electron Energy States

Electrons... Adapted from Fig. 2.4, Callister &

Rethwisch 8e.
• have discrete energy states

• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d

4s

3p M-shell n = 3
Energy
3s

2p
L-shell n = 2
2s

1s K-shell n = 1

11
Electronic configuration
(Pauli
Element
exclusion Principle)
Atomic #Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 22s 1
Beryllium 4 1s 22s2
Boron 5 1s 22s 22p 1 Valence
Carbon 6 1s 22s 22p 2 （ outer most shell)
... ...
Neon 10 1s 22s 22p 6 (stable)
Sodium 11 1s 22s 22p 63s 1
Magnesium 12 1s 22s 22p 63s 2 Adapted from Table
Aluminum 13 1s 22s 22p 63s 23p 1 2.2, Callister &
Rethwisch 8e.
... ...
Argon 18 1s 22s 22p 63s 23p 6 (stable)
... ... ...
Krypton 36 1s 22s 22p 63s 23p 63d 10 4s 24p 6 (stable)

P12
Periodic table
Alkaline metals Halogens

inert gases
-
give up 1e Alkaline earth metals

-
accept 2e

accept 1e
-
give up 2e
-
give up 3e

Transition metals
H He

Li Be O F Ne

Adapted from Fig.

Na Mg S Cl Ar
2.6, Callister &

K Ca Sc Se Br Kr Rethwisch 8e.

Rb Sr Y Te I Xe

Cs Ba Po At Rn

Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons

to become + ions. to become - ions.

P13
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

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 Primary bonding – ionic
• Transfer of electrons
Electrostatic (coulombic) force
• Difference of electronegativity

Na (metal) Cl (nonmetal)
11 17
unstable unstable
electron

Na (cation)
stable
+ - Cl (anion)
Coulombic stable
Attraction

Charge-charge interaction
P16
Bonding energy
r
E A FA dr

r
ER FR dr integrating

r
EN FN dr

Minimum

P17
Ionic bond – metal + nonmetal
donates accepts
electrons electrons

Dissimilar electronegativities

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

[Ne] 3s2

2+ 2 2 6 2- 2 2 6
Mg 1s 2s 2p O 1s 2s 2p

[Ne] [Ne]

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Primary bonding - ionic

Nondirectional bonding
(in all directions same
magnitude of the bond)

Source: textbook.

P19
Primary bonding - ionic
• Predominant bonding in Ceramics
Numbers indicate
NaCl
MgO electronegativity
CaF 2
CsCl

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.

P20
Primary bonding - ionic

Repulsive energy ER

A
E A 
r Interatomic separation r

B Net energy EN
ER  n
r
Adapted from
Fig. 2.8(b),
Callister &
Rethwisch 8e.

Attractive energy EA

P21
Primary bonding - ionic
Permittivity of vacuum 8.85 x Valences of ions
10-12 F/m

1
A Z1e Z 2e 
4 0

Electron charge = 1 eV = 1.602 x 10-19 j

• Valence of ion = number of e- lost or gained

P22
Covalent Bonding
• similar electronegativity: share electrons
• bonds determined by valence – s & p orbitals dominate
bonding
• Example: CH4

C: has 4 valence e-, H

shared electrons

needs 4 more CH 4
from carbon atom

H: has 1 valence e-,

needs 1 more H C H

Electronegativities shared electrons

from hydrogen
are comparable. H
atoms
Adapted from Fig. 2.10, Callister & Rethwisch 8e.

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 Covalent Bonding

•Bonds maybe very strong like Diamond

(Tm>3550oC) and weak like Bismuth (Tm~270oC)
[elemental solids, e.g. Si, Ge & compounds made
of different elements at the right side of Periodic
table, e.g. InAs]

•Possible to have partially ionic and partially

covalent bonding (depends on the χ electronegativity
difference)
•Other types of covalent molecules: elemental molecules
(H2, F2, Cl2) or dissimilar atoms molecules (e.g. H2O, HF)
•Mechanical behaviors of these materials vary
widely: some are relatively strong, others are
weak; some fail in a brittle manner, whereas
others experience significant amounts of
deformation before failure. It is difficult to predict
the mechanical
P24 properties of covalently bonded
Metallic Bonding

Metallic bonding, the final primary bonding type, is found in

metals and their alloys.

A relatively simple model has been proposed for the bonding

scheme:
With this model, these valence electrons are not bound to any
particular atom in the solid and are more or less free to drift
throughout the entire metal. They may be thought of as
belonging to the metal as a whole, or forming a “sea of
electrons” or an “electron cloud.”

The remaining non valence (core) electrons and atomic nuclei

form what are called ion cores
 Metallic Bonding
Metallic Bonding

•Conductivity in metals is because of free electrons.

•Metallic bonding is found in the periodic table for
Group IA and IIA elements and, in fact, for all
elemental metals.

P26
 Van der Waals Bonds (Secondary Bonds)
• Van der Waals interaction is the principal attractive
interaction in crystals of inert gases (interatomic
bonds) and organic molecules (intermolecular bonds)

• The VdW bonds arise because two atoms (or

molecules) induce a dipole moment in each other
which causes a distortion in the charge distribution
and gives rise to a induced dipole-dipole interaction,
and electrostatic attraction
SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating Induced dipole bonds
asymmetric electron ex: liquid H 2
clouds H 2 H 2

+ - + - H H H H
secondary secondary
Adapted from Fig. 2.13, Callister &

bonding Rethwisch 8e.

bonding

Polar molecule-Induced dipole bonds

• Permanent dipole bonds

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Properties from Bonding: Tm
Properties from Bonding: α

The coefficient of thermal

expansion describes how the
size of an object changes with
a change in temperature.

Why? (what larger ‘a’

means???
Properties from Bonding: Ε
 Secondary Bonding

•Seconda
ry bonds
weak as
compared
to primary
bonds

P32
Summary: Primary Bonds

Ceramics Large bond energy

(Ionic & covalent bonding):

Metals Variable bond energy

(Metallic bonding):

Polymers Directional Properties

Secondary bonding dominates

(Covalent & Secondary):

seco
n da r y
bond
ing

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