Chapter 2: Atomic Structure &

Interatomic Bonding

ISSUES TO ADDRESS...
• What characteristics of atoms/molecules
promote interatomic/intermolecular bonding?
• What types of interatomic/intermolecular
bonds exist ?
• What properties of materials depend on the
magnitude of interatomic/intermolecular bonds ?

Chapter 2 - 1
 Atomic Structure (Freshman Chem.)
• 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 in neutral species

A = Atomic wt (or mass) = wt of 6.022 x 1023 molecules or

atoms

Chapter 2 - 2
 Atomic Structure (cont.)
• Some of the following properties are
determined by an atom's electronic structure:
1) Chemical
2) Electrical
3) Thermal
4) Optical

Chapter 2 - 3
 Electronic Structure
This picture looks like a mini planetary
system. But quantum mechanics tells
us that this analogy is not correct:

Electrons move not in circular orbits, but in 'fuzzy‘ orbits.

Actually, we cannot tell how it moves, but only can say what
is the probability of finding it at some distance from the
nucleus. Electrons behave like a “cloud”

Only certain “orbits” or shells of electron probability densities

are allowed. The shells are identified by a principal
quantum number n, which can be related to the size of the
shell, n = 1 is the smallest; n = 2, 3 .. are larger.

Chapter 2 - 4
 Electronic Structure
• Electrons have wave-like and particle-like
characteristics.
• Two wave-like characteristics are
– Electron position in terms of probability density
– shape, size, orientation of probability density
determined by quantum numbers
Quantum # Designation/Values
n = principal (shell) K, L, M, N, O (1, 2, 3, 4, etc.)
l = subshell s, p, d, f
ml = no. of orbitals 1, 3, 5, 7
ms = spin ½, -½
Each “orbit” or shell can accommodate up to a maximum number of
electrons. The most inner K-shell can accommodate up to two electrons,
called s-electrons; the next L-shell two s-electrons and six p-electrons;
the M-shell can host two s-electrons, six p-electrons, and ten d-electrons,
and so on.
Chapter 2 - 5
 Electron Energy States
Electrons...
• have discrete energy values
• tend to occupy lowest available energy states

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
Chapter 2 - 6
 SURVEY OF ELEMENTS
• Most elements: Electron configurations 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
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
... ...
Chlorine 17 1s 2 2s 2 2p 6 3s 2 3p 5
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 not stable?

Chapter 2 - 7
 Electron Configurations
• Filled shells are more stable – require more
energy to gain or lose electrons
• Valence electrons – those in outer unfilled
shells
• Valence electrons available for bonding and
tend to determine an atom’s chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

4 valence electrons

Chapter 2 - 8
 Electronic Configurations (cont.)
ex: Fe (atomic # = 26)
Electron configuration 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 9
 The Periodic Table
• Elements in each column: Similar valence electron structure

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

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

H He
Li Be O F Ne
Na Mg S Cl Ar
K Ca Sc Se Br Kr
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. Chapter 2 - 10
 Electronegativity
• Large values: tendency to acquire electrons.

Chapter 2 - 11
 Ionization Process
metal atom + nonmetal atom

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]”

But, sure, Mg2+ and O are not Ne. Why?

Chapter 2 - 12
 Types of Bonding
Primary bonding: e- are transferred or shared
Strong energy bonds (100-1000 KJ/mol or 1-10 eV*/atom)

Ionic: Strong Coulomb interaction among negative species (have extra electrons)
and positive ones (having lost electrons). Example: Na+Cl-

Covalent: electrons are shared between the molecules, to saturate the valency. Example - H2

Metallic: the atoms are ionized, loosing some electrons from the valence band. Those
electrons form a electron cloud, which binds the charged nuclei in place

Secondary Bonding: no e- transferred or shared. Interaction of atomic/molecular dipoles

Weak (< 100 KJ/mol or < 1 eV/atom)
Fluctuating Induced Dipole (inert gases, H2, Cl2…)
Permanent dipole bonds (polar molecules - H2O, HCl...)

*The electron volt (eV) – energy unit convenient for description of atomic bonding
One Electron volt is the energy lost / gained by an electron when it is taken through
a potential difference of one volt.
E = q × V with q = 1.6 x 10-19 Coulombs and V = 1 volt ; 1 eV = 1.6 x 10-19 J Chapter 2 - 13
 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 stable

Once they are ions…

Coulombic Attraction Chapter 2 - 14
 Ionic Bonding (cont.)
the interaction between two atoms
due to the opposite charges (coulombic attraction),
as the interatomic distance decreases,
the attractive force increases
r0

The balance between attractive and repulsive forces,

f = 0, determines the equilibrium interatomic distance r0

If the atoms get too close,

repulsive forces appear. Why?

We can thus see that the equilibrium separation

corresponds to a minimum of the net energy (EO)

the larger EO, the stronger the bond

and the more stable the system

although presented here in the frame of ionic bonding, the same

kind of behavior appears for other types of bonds, with different
attractive forces. The nature of the repulsive forces remains the
same 15
Chapter 2 -
 Ionic Bonding (cont.)
Predominant bonding in Ceramics
Examples:
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 - 16
 Covalent Bonding
• Similar electronegativities  share electrons
• Bonds involve valence electrons – normally s and p
orbitals are involved
Example: H2 Electronegativities are the same.

Each H: has 1 valence e-, H H

needs 1 more to fill the shell

H2

H H

shared 1s electron shared 1s electron

from 1st hydrogen from 1st hydrogen
atom atom Chapter 2 - 17
 Covalent Bonding: a bit more of it

In covalent bonding, electrons are shared between the molecules, so as to

saturate the valency. Note that the electrons are not transferred as in the ionic bonding,
but they are localized between the neighboring ions and form directional bond between them.
- Cooperative sharing of valence electrons
- Can be described by the overlap of the orbitals of the shared electrons
- Covalent bonds are thus HIGHLY directional (direction of the overlapped orbital)
- Covalent bond model: an atom can covalently bond with at most 8-N’,
N’ = number of valence electrons

Example: Cl2 molecule. ZCl =17 (1s2 2s2 2p6 3s2 3p5)
N’ = 7, 8 - N’ = 1 → can form only one covalent bond

Chapter 2 - 18
 Covalent Bonding: the (important) case of Carbon
Carbon materials. Z = 6 (1s2 2s2 2p2) N’ = 4, 8 - N’ = 4 → can form up to four covalent bonds

Methane

the directional
character
of covalent bonds

Ethylene

Polyethylene

2-D schematic plot of the

spaghetti-like structure
of solid polyethyleneChapter 2 - 19
 Carbon

1s2 2s2 2p2 1s2 2s2 2p6

diamond: each C atom has four covalent bonds with

four other carbon atoms:
a hugely tighten structure !!

The directional organization of the covalent

bonds yields the well-known tetrahedral structure of
diamonds and other carbon-built materials (graphite, …)

Chapter 2 - 20
 Metallic Bonding
Valence electrons are detached from atoms, and spread in
an 'electron cloud' that "glues" the positive ions together.

Unlikely to covalent, metallic bonds are ensured by mobile electrons and

are hence non-directional. They form and hold in any direction, which means
the bonds do not “break” when atoms are rearranged: ductility

metals can experience a significant degree

of plastic deformation (formability)

Chapter 2 - 21
 Mixed Bonding
• Most common mixed bonding type is Covalent-Ionic
mixed bonding

% ionic character = x (100%)

where XA & XB are electronegativities of the two

elements participating in the bond
Ex: MgO XMg = 1.2
XO = 3.5

æ -
(3.5-1.2)2 ö
ç
% ionic character = 1- e 4 ÷ x (100%) = 73.3%
ç ÷
è ø
Chapter 2 - 22
 Secondary Bonding
Secondary (van der Waals) bonds are physical bonding
(as opposite to chemical bonding that involves e- transfer or sharing)
Arise from attractive forces between dipoles (permanent or fluctuating)

Very weak bond energy, ~0.1 eV/atom or ~10 kJ/mol, compared

to primary bonding (50 to 1000 kJ/mol)

- Permanent dipoles (polar molecules)

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl
but the strongest among secondary
bonds
-ex: polymer (permanent dipoles)
linear polymer molecule
(primary bonding)
Chapter 2 - 23
A special case: the hydrogen bonds - secondary bond formed between two
permanent dipoles in adjacent water molecules

primary strong bonds

inside the molecule

secondary weak bonds

between molecule

Chapter 2 - 24
 - Fluctuating dipoles (non-polar molecules)
Even in electrically symmetric molecules/atoms an electric dipole can be created by random
fluctuations of the electron density distribution.
5. That replicates through the
1. in average, 2. but instantaneous 3. are felt by the e- of an ensemble of molecules
e- are evenly random asymmetries adjacent molecule that
distributed of e- distribution runs asymmetric as well

4. creating a
fluctuating dipole
bonds due to these fluctuating
induced dipoles are the weakest (inert gases, H2, Cl2).

This is why polar molecules have higher melting points than non-polar ones

Chapter 2 - 25
 Properties Related to Bonding I:
Melting Temperature (Tm)
• Bond length, r0 • Melting Temperature, Tm
Energy

• Bond energy, Eo ro
r
Energy
smaller Tm
unstretched length
ro larger Tm
r
Eo = The larger Eo, the higher Tm
“bond energy”
Chapter 2 - 26
 Properties Related to Bonding II:
Coefficient of Thermal Expansion (al)
• Coefficient of thermal expansion, al
length, L o ΔL
= αl (T2 -T1)
unheated, T1 Lo
ΔL
heated, T 2

unstretched length
Energy

ro
r
The smaller Eo, the larger αl.
Eo
larger αl

Eo smaller αl
Chapter 2 - 27
 Summary: Properties Related to
Bonding Type and Bonding Energy
Ceramics Large bond energy
(Ionic & covalent bonding): high Tm
large E
small αl

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate αl

Polymers Weak bond energy (between chains)

(Covalent & Secondary): Secondary bonding responsible for
most physical properties
low Tm
small E
large αl
Chapter 2 - 28
 SUMMARY
• A material’s chemical, electrical, thermal, and optical
properties are determined by electronic configuration.
• Valence electrons occupy the outermost unfilled
electron shell.
• Primary bonding types include covalent, ionic, and
metallic bonding.
• Secondary or van der Waals bonds are weaker than
the primary bonding types.
• The percent ionic character of a covalent-ionic mixed
bond between two elements depends on their
electronegativities.

Chapter 2 - 29