Atomic Structure & Interatomic Bonding

Chapter 2 - 1
Atomic Structure & Interatomic Bonding
WHY STUDY Atomic Structure and Interatomic
Bonding?
• An important reason to have an understanding
of interatomic bonding in solids is that in some
instances, the type of bond allows us to explain
a material’s properties.

• For example, consider carbon, which may exist

as both graphite and diamond. Whereas
graphite is relatively soft and has a “greasy” feel
to it, diamond is one of the hardest known
materials in nature Chapter 2 - 2
Atomic Structure & Interatomic Bonding
WHY STUDY Atomic Structure and Interatomic
Bonding?
• In addition, the electrical properties of diamond
and graphite are dissimilar: diamond is a poor
conductor of electricity, but graphite is a
reasonably good conductor.

• These disparities in properties are directly

attributable to a type of interatomic bonding
found in graphite that does not exist in diamond

Chapter 2 - 3
Atomic Structure & Interatomic Bonding
Lecture Learning Objectives

you should be able to do the following:

1.Name the two atomic models cited, and note the differences
between them.

2.Describe the important quantum-mechanical principle that

relates to electron energies.

3.(a) Schematically plot attractive, repulsive, and net energies

versus interatomic separation for two atoms or ions.
(b) Note on this plot the equilibrium separation and the
bonding energy.
Chapter 2 - 4
Atomic Structure & Interatomic Bonding

Lecture Learning Objectives

you should be able to do the following:

4. (a) Briefly describe ionic, covalent, metallic, hydrogen, and

van der Waals bonds.
(b) Note which materials exhibit each of these bonding types.

Chapter 2 - 5
Atomic Structure & Interatomic Bonding

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

Chapter 2 - 6
 Atomic Structure (Freshman Chem.)
• 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 of 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 = 1g/mol

C 12.011
H 1.008 etc.
Chapter 2 - 7
AVAGADRO’S NUMBER = 6.022 x 1023 = NA

ATOMIC OR MOLECULAR WEIGHT =

NAxW EI
G HT P
ER ATOM.

number of neutrons = N
number of protons = Z
A= Z + N (2.1)

Chapter 2 - 8
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
5) Mechanical

Chapter 2 - 9
Atomic Structure

Chapter 2 - 10
BOHR MODEL OF ATOM

Chapter 2 - 11
WAVE MECHANICAL MODEL OF ATOM

Chapter 2 - 12
 Electronic Structure
• Electrons have wavelike and particulate
properties.
– This means that 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.)
l = subsidiary (orbitals) s ,p ,d ,f (0, 1, 2, 3,…,n -1)
ml = ma gne ti
c 1 ,3,
5 ,7 (l
- to l
+)
ms
=s
p
i
n ½
,
-
½

Chapter 2 - 13
Electronic Structure

Chapter 2 - 14
Electronic Structure

Chapter 2 - 15
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N -shell n = 4

3d
4s

Energy 3p M -shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L -shell n = 2
2s

1s K -shell n = 1
Chapter 2 - 16
Electron Energy States

Chapter 2 - 17
Electron Energy States

Chapter 2 - 18
 Electron Energy States
• Pauli exclusion principle, another quantum-mechanical
concept, which stipulates that each electron state can hold no
more than two electrons that must have opposite spins.

• Thus, s, p, d, and f subshells may each accomodate,

respectively, a total of 2, 6, 10, and 14 electrons;

Chapter 2 - 19
 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 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
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.
Chapter 2 - 20
 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 and
physical properties

– example: C (atomic number = 6)

1s 2 2s 2 2p 2

valence electrons

Chapter 2 - 21
 Electronic Configurations
ex: Fe - atomic # = 26 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6 4s 2

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

Energy 3p M -shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L -shell n = 2
2s

1s K -shell n = 1

Chapter 2 - 22
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e -

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

H He

Li Be O F Ne

Na Mg S Cl Ar Adapted from
Fig. 2.6,
K Ca Sc Se Br Kr Callister &
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
Chapter 2 - 23
to become + ions. to become - ions.
 Electronegativity

Smaller electronegativity Larger electronegativity

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.

Chapter 2 - 24
Electrons in different shells

Chapter 2 - 25
Electrons in some selected elements

Chapter 2 - 26
Electrons in some selected elements

Chapter 2 - 27
FORCES AND ENERGIES

Chapter 2 - 28
FORCES AND ENERGIES

Chapter 2 - 29
 Properties From Bonding:Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, E o r o
r
Energy smallerTm

unstretched length
r o largerTm
r
Eo = Tm
i
s
la
r
gE
e
r
i
fi
sl
a
r
ge
r.
o
“bond energy”

Chapter 2 - 30
 Properties From Bonding : 
• Coefficient of thermal expansion, 
length,L o coeff. thermal expansion
unheated,T 1
L L
=  (T 2 -T 1)
heated,T 2 Lo

•  ~ symmetric atr o
Energy
unstretched length
ro
r  is larger ifE o
i
s
sm
al
l
e
r.

Eo
larger 

Eo smaller 
Chapter 2 - 31
 FORCES AND ENERGIES
• The magnitude of this bonding energy and the shape of the
energy–versus–interatomic separation curve vary from
material to material, and they both depend on the type of
atomic bonding.

• Material properties depend on E0

,
t
hec
u
r
v
es
h
a
pe
,
an
d
bo
n ding t
y pe.

• For example, materials having large bonding energies

typically also have high melting temperatures; at room
temperature, solid substances are formed for large bonding
energies, whereas for small energies, the gaseous state is
favored; liquids prevail when the energies are of intermediate
magnitude.
Chapter 2 - 32
 FORCES AND ENERGIES
• The mechanical stiffness (or modulus of elasticity) of a
material is dependent on the shape of its force–versus–
interatomic separation curve.

• The slope for a relatively stiff material at the r = r0

p
o
si
t
i
on
on
thec urvew il
l be q uite stee p ;slo
p es ar es hallo w er
f
o
rm
or
e
flexiblem a teri
a ls.

• How much a material expands upon heating or contracts

upon cooling (i.e., its linear coefficient of thermal expansion)
is related to the shape of its E–versus–r curve.

• A deep and narrow “trough,” which typically occurs for

materials having large bonding energies, normally correlates
with a low coefficient of thermal expansion and relatively
small dimensional alterations for changes in temperature
Chapter 2 - 33
FORCES AND ENERGIES

Chapter 2 - 34
FORCES AND ENERGIES

Chapter 2 - 35
FORCES AND ENERGIES

Chapter 2 - 36
 ATOMIC BONDING
• Three different types of primary or chemical bond are found
in solids—ionic, covalent, and metallic.

• For each type, the bonding necessarily involves the valence

electrons; furthermore, the nature of the bond depends on
the electron structures of the constituent atoms.

• In general, each of these three types of bonding arises from

the tendency of the atoms to assume stable electron
structures, like those of the inert gases, by completely filling
the outermost electron shell.

Chapter 2 - 37
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons
 
Dissimilar electronegativities  

ex: MgO Mg 1s 2 2s 2 2p 6 3s 2 O 1s 2 2s 2 2p 4
[Ne] 3s 2 

Mg2+ 1s 2 2s 2 2p 6 O2- 1s 2 2s 2 2p 6
[Ne] [Ne]

Chapter 2 - 38
 Ionic Bonding
• Occurs between + and – ions (composed of both
metallic and nonmetallic elements
• 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 Chapter 2 - 39
Ionic Bonding

Chapter 2 - 40
Ionic Bonding

Chapter 2 - 41
 Ionic Bonding
• Ionic bonding is termed non-directional—that is, the
magnitude of the bond is equal in all directions
around an ion.

• It follows that for ionic materials to be stable, all

positive ions must have as nearest neighbors
negatively charged ions in a three-dimensional
scheme, and vice versa.

Chapter 2 - 42
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

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.

Chapter 2 - 43
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s &p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valencee - , CH 4
from carbon atom
needs 4 more

H: has 1 valencee - , H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10,Callister & Rethwisch 8e.

Chapter 2 - 44
 Covalent Bonding

Schematic representation of
covalent bonding in a molecule
of hydrogen (H2)
.

Chapter 2 - 45
 Covalent Bonding
• Covalent bonding, is found in materials whose atoms have
small differences in electronegativity—that is, that lie near
one another in the periodic table.

• For these materials, stable electron configurations are

assumed by the sharing of electrons between adjacent
atoms.

• Two covalently bonded atoms will each contribute at least

one electron to the bond, and the shared electrons may be
considered to belong to both atoms.

Chapter 2 - 46
 Covalent Bonding
• There is an overlapping of electron orbitals in the region
between the two bonding atoms.

• The covalent bond is directional—that is, it is between

specific atoms and may exist only in the direction between
one atom and another that participates in the electron
sharing.

• Many nonmetallic elemental molecules (e.g., Cl2, F2), as well

as molecules containing dissimilar atoms, such as CH4, H2O,
HNO3, and HF, are covalently bonded.

Chapter 2 - 47
 Metallic Bonding
• Metallic bonding, the final primary bonding type, is found in
metals and their alloys.

• A relatively simple model has been proposed that very nearly

approximates 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.

Chapter 2 - 48
 Metallic Bonding
• We note that at room temperature, most metals and their
alloys fail in a ductile manner—that is, fracture occurs after
the materials have experienced significant degrees of
permanent deformation.

• This behavior is explained in terms of deformation

mechanism, which is implicitly related to the characteristics
of the metallic bond.

Chapter 2 - 49
 Metallic Bonding

Schematic illustration of metallic bonding.

Chapter 2 - 50
 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. 2.13,
bonding
Callister & Rethwisch 8e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding
H Cl

secon
-ex: polymer da r y b on secondary bonding
ding

Chapter 2 - 51
 Secondary Bonding or
Van Der Waals Bonding
• Secondary bonds, or van der Waals (physical) bonds, are
weak in comparison to the primary or chemical bonds;
bonding energies range between about 4 and 30 kJ/mol

• Secondary bonding exists between virtually all atoms or

molecules, but its presence may be obscured if any of the
three primary bonding types is present.

• Secondary bonding is evidenced for the inert gases, which

have stable electron structures.

Chapter 2 - 52
 Secondary Bonding or
Van Der Waals Bonding
• In addition, secondary (or intermolecular) bonds are
possible between atoms or groups of atoms, which
themselves are joined together by primary (or
intramolecular) ionic or covalent bonds.

• Secondary bonding forces arise from atomic or molecular

dipoles.

• In essence, an electric dipole exists whenever there is some

separation of positive and negative portions of an atom or
molecule.

Chapter 2 - 53
 Secondary Bonding or
Van Der Waals Bonding
• The bonding results from the coulombic attraction between
the positive end of one dipole and the negative region of an
adjacent one.

• Hydrogen bonding, a special type of secondary bonding, is

found to exist between some molecules that have hydrogen
as one of the constituents. These bonding mechanisms are
discussed briefly next.

Chapter 2 - 54
 Secondary Bonding or
Van Der Waals Bonding
• Dipole interactions occur between:

Fluctuating Induced Dipole Bonds

Chapter 2 - 55
 Secondary Bonding or
Van Der Waals Bonding
• The liquefaction and, in some cases, the solidification of
the inert gases and other electrically neutral and symmetric
molecules such as H2 an dC l
2a rere a l
ized be caus eof
this
type o fb ondi
ng .

• Melting and boiling temperatures are extremely low in

materials for which induced dipole bonding predominates;
of all possible intermolecular bonds, these are the weakest.
Bonding energies and melting temperatures for argon,
krypton, methane, and chlorine are low

Chapter 2 - 56
 Secondary Bonding or
Van Der Waals Bonding
• Dipole interactions occur between:

Polar Molecule–Induced Dipole Bonds

• Permanent dipole moments exist in some molecules by

virtue of an asymmetrical arrangement of positively and
negatively charged regions; such molecules are termed
polar molecules, e.g. HCl molecule

Chapter 2 - 57
 Secondary Bonding or
Van Der Waals Bonding
• Dipole interactions occur between:

Permanent Dipole Bonds

• Coulombic forces also exist between adjacent polar

molecules.

• The associated bonding energies are significantly greater

than for bonds involving induced dipoles.

Chapter 2 - 58
 Secondary Bonding or
Van Der Waals Bonding
• The strongest secondary bonding type, the hydrogen bond,
is a special case of polar molecule bonding.

• It occurs between molecules in which hydrogen is

covalently bonded to fluorine (as in HF), oxygen (as in H2
O
)
,
o r n
itr
og en (a
s i
n NH 3)
.

• For each H - F, H - O, or H - N bond, the single hydrogen

electron is shared with the other atom.

Chapter 2 - 59
 Secondary Bonding or
Van Der Waals Bonding
• Thus, the hydrogen end of the bond is essentially a positively
charged bare proton unscreened by any electrons.

Chapter 2 - 60
 Mixed Bonding
• The atomic bonds are mixtures of two or more of these
extremes (i.e., mixed bonds).

• Three mixed- bond types—covalent–ionic, covalent–metallic,

etc.
• For mixed covalent–ionic bonds, there is some ionic
character to most covalent bonds and some covalent
character to ionic ones.

Chapter 2 - 61
 Mixed Bonding
• As such, there is a continuum between these two extreme
bond types.

• The degree of either bond type depends on the relative

positions of the constituent atoms in the periodic table.

• The wider the separation (both horizontally—relative to Group

IVA—and vertically) from the lower left to the upper right
corner (i.e., the greater the difference in electronegativity), the
more ionic is the bond.

Chapter 2 - 62
 Mixed Bonding
• Conversely, the closer the atoms are together (i.e., the
smaller the difference in electronegativity), the greater is the
degree of covalency.

• Percent ionic character (%IC) of a bond between elements A

and B (A being the most electronegative) may be
approximated by the expression:

• Another type of mixed bond is found for some elements in

Groups IIIA, IVA, and VA of the periodic table (viz., B, Si, Ge, As,
Sb, Te, Po, and At)
Chapter 2 - 63
Mixed Bonding

Chapter 2 - 64
 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)
inter-molecular
Chapter 2 - 65
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
smallTm
secon smallE
da r y b on
ding
large 

Chapter 2 - 66
 SUMMARY
• The two atomic models are Bohr and wave mechanical.
Reading:
Whereas the Bohr model assumes electrons to be particles
orbiting the nucleus in discrete paths, in wave mechanics we
consider them to be wavelike and treat electron position in
terms
CoreofProblems:
a probability distribution.

• The energies of electrons are quantized—that is, only specific

values of energy are allowed.
Self-help Problems:
• The four electron quantum numbers are n, l, ml
,
and
m
.
s

Chapter 2 - 67
 SUMMARY
• They specify, respectively, electron orbital size, orbital shape,
Reading:
number of electron orbitals, and spin moment.

• According to the Pauli exclusion principle, each electron state

can accommodate
Core Problems: no more than two electrons, which must
have opposite spins.

• Elements in each of the columns (or groups) of the periodic

Self-help
table Problems:
have distinctive electron configurations. For example:
Group 0 elements (the inert gases) have filled electron shells.
Group IA elements (the alkali metals) have one electron
greater than a filled electron shell.

Chapter 2 - 68
 SUMMARY
• Bonding force and bonding energy are related to one another.
Reading:
• Attractive, repulsive, and net energies for two atoms or ions
depend on interatomic separation
Core Problems:
• From a plot of interatomic separation versus force for two
atoms/ions, the equilibrium separation corresponds to the
value at zero force.
Self-help Problems:
• From a plot of interatomic separation versus potential energy
for two atoms/ions, the bonding energy corresponds to the
energy value at the minimum of the curve.

Chapter 2 - 69
 SUMMARY
• For ionic bonds, electrically charged ions are formed by the
Reading: of valence electrons from one atom type to
transference
another.

• There
CoreisProblems:
a sharing of valence electrons between adjacent
atoms when bonding is covalent.

• With metallic bonding, the valence electrons form a “sea of

Self-helpthat
electrons” Problems:
is uniformly dispersed around the metal ion
cores and acts as a form of glue for them.

Chapter 2 - 70
 SUMMARY
• Relatively weak van der Waals bonds result from attractive
Reading:
forces between electric dipoles, which may be induced or
permanent.

• For hydrogen
Core bonding, highly polar molecules form when
Problems:
hydrogen covalently bonds to a nonmetallic element such as
fluorine.

Self-help Problems:

Chapter 2 - 71
 SUMMARY
• In addition to van der Waals bonding and the three primary
Reading:
bonding types, covalent– ionic, covalent–metallic, and
metallic–ionic mixed bonds exist.

• The percent
Core ionic character (%IC) of a bond between two
Problems:
elements (A and B) depends on their electronegativities (X’s)

Self-help Problems:

Chapter 2 - 72
 SUMMARY
• Correlations between bonding type and material class were
Reading:
noted:

• Polymers—covalent
Core Problems:
• Metals—metallic

• Ceramics—ionic/mixed ionic–covalent
Self-help Problems:
• Molecular solids—van der Waals

• Semi-metals—mixed covalent–metallic

• Intermetallics—mixed metallic–ionic

Chapter 2 - 73