Chapter 2

Atomic and crystalline structures

1
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 the hardest known
material. This dramatic disparity in properties is directly
attributable to a type of interatomic bonding found in
graphite that does not exist in diamond 2
The crystal structure of diamond The structure of graphite.

• Some of the important properties of solid materials

depend on geometrical atomic arrangements, and also the
interactions that exist among constituent atoms or
molecules.
3
Atomic Structure
• Each atom consists of a very small nucleus composed of protons
and neutrons, which is encircled by moving electrons. Both
electrons and protons are electrically charged, the charge
magnitude being 1.60 10-19 C which is negative in sign for
electrons and positive for protons; neutrons are electrically
neutral.
• atomic number- Each chemical element is characterized by the
number of protons in the nucleus, or the atomic number (Z). For
an electrically neutral or complete atom, the atomic number also
equals the number of electrons. 4
• The atomic mass (A) of a specific atom may be expressed
as the sum of the masses of protons and neutrons within
the nucleus. Although the number of protons is the same
for all atoms of a given element, the number of neutrons
(N) may be variable. Thus atoms of some elements have
two or more different atomic masses, which are called
isotopes.

5
• Mole - In one mole of a substance there are 6.023x1023
(Avogadro’s number) atoms or molecules. These two
atomic weight schemes are related through the following
equation: 1 amu/atom (or molecule) = 1 g/mol
• For example, the atomic weight of iron is 55.85
amu/atom, or 55.85 g/mol
Electrons in atoms
• Atomic Models

6
• Bohr atomic model - in which electrons are assumed to
revolve around the atomic nucleus in discrete orbitals,
and the position of any particular electron is more or less
well defined in terms of its orbital

Schematic representation of the Bohr atom.

7
Bohr atomic model
1. e- can have only specific (quantized) energy values
2. light is emitted as e- moves from one energy level to a
lower energy level

En = -RH ( 12 )
n

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x 10-18J
8
The Bohr Model of the Atom

9
The Bohr Model of the Atom: Ground and Excited States

• In the Bohr model of hydrogen, the lowest amount of

energy hydrogen’s one electron can have corresponds to
being in the n = 1 orbit. We call this its ground state.
• When the atom gains energy, the electron leaps to a
higher energy orbit. We call this an excited state.
• The atom is less stable in an excited state and so it will
release the extra energy to return to the ground state.
– Either all at once or in several steps.
10
 Line Emission Spectrum of Hydrogen Atoms

Every element has a unique emission spectrum

11
The Bohr Model of the Atom: Hydrogen Spectrum
• Every hydrogen atom has identical orbits, so every hydrogen
atom can undergo the same energy transitions.
• However, since the distances between the orbits in an atom are
not all the same, no two leaps in an atom will have the same
energy.
– The closer the orbits are in energy, the lower the energy of the
photon emitted.
– Lower energy photon = longer wavelength.
• Therefore, we get an emission spectrum that has a lot of lines that
are unique to hydrogen. 12
The Bohr Model of the Atom:
Hydrogen Spectrum

13
 Bohr showed the energy a H
atom can have is equal to:

1
( 2)
En = -RH
n
Ephoton = DE = Ef - Ei
1
Ef = -RH ( 2 )
n
f
( 1 )
Ei = -RH
n2
i
(1 1)
DE = RH 2
n n2
i f
Where: RH is the Rydberg constant
n is the principal quantum number 14
Example: A hydrogen atom exists with its electron with in
the n=3 state. The electron undergoes a transition to n=2
state.
Calculate a. the energy of the corresponding photon
b. its frequency and wave length
c. the energy absorbed or emitted and
d. which series does it belong to what specific
type of emission does it represent ?

15
wave-mechanical model - This Bohr model was eventually
found to have some significant limitations because of its
inability to explain several phenomena involving electrons.
A resolution was reached with a wave-mechanical model, in
which the electron is considered to exhibit both wave-like
and particle-like characteristics.
With this model, an electron is no longer treated as a particle
moving in a discrete orbital; rather, position is considered to
be the probability of an electron’s being at various locations
around the nucleus. 16
Comparison of the
(a) Bohr and
(b) wave-mechanical atom
models in terms of electron
distribution

17
Quantum Numbers - Using wave mechanics, every electron in an atom is
characterized by four parameters called quantum numbers.
– Quantum mechanics describes the energy levels of an electron wave with
four quantum numbers.
• distance from nucleus

• energy sublevel

• orientation in space.

• direction of spin

– Principal quantum number (n)

• Describes main energy level of the electron in terms of its distance

from the nucleus.
• n = 1, 2, 3, 4, 5, 6, 7 18
– Angular momentum quantum number (l)
• Defines energy sublevels within the main energy levels

• s, p, d, or f designating the type of orbital and also the

orbital shape.
• l represented by integer ranging from 0 to n-1
• The Heisenberg Uncertainty Principle states that you
cannot measure the momentum and exact position of an
electron at the same time.
– What you can measure is the probability that an electron
will be found in a certain area, called an orbital.
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(A)An electron distribution sketch representing probability regions
where an electron is most likely to be found. (B) A boundary surface,
or contour, that encloses about 90 percent of the electron distribution
shown in (A). This three-dimensional space around the nucleus,
where there is the greatest probability of finding an electron, is called
an orbital. 20
– Magnetic quantum number (ml)
• Defines the orientation in space of the orbitals
relative to an electrical field.
• For every subshell, l, there are 2l+1 orbitals
• The s orbital has one orientation
• The p sublevel can have 3 orientations
• The d sublevel can have 5 orientations
• The f sublevel can have 7 orientations.

21
• There are three
possible orientations of
the p orbital, and these
are called px, py, and pz.
Each orbital can hold
two electrons, so a
total of six electrons
are possible in the
three orientations; thus
the notation p6.
22
 – Spin quantum number (ms)
• Describes the direction of spin of an electron in its
orbit.
• Electrons occur in pairs and each of the orientations
for a sublevel can have one electron pair.
• Experimental
evidence supports the
concept that electrons
can be considered to
spin one way or the
other as they move
about an orbital under
an external magnetic
field.
23
• The Number of Available Electron States in Some of the
Electron Shells and Subshells

24
Electron Energy States
Electrons
- have discrete energy states
- tend to occupy lowest available energy state
4d
Can hold up to 32
4p N-shell n = 4 electrons

3d
4s
Can hold up to 18
Energy 3p M-shell n = 3 Electrons
3s

2p L-shell n = 2 Can hold up to 8

2s electrons

Can hold up to 2
1s K-shell n = 1 electrons
25
 – Pauli Exclusion Principle
• No two electrons can have the same set of quantum
numbers.
• At least one of the quantum numbers must differ.
Electron Configuration
This is a shorthand designation for electron orientation.
The lowest possible energy level is n=1.
If one electron already occupies this energy level, a second
can only occupy it if it has a different spin quantum number.
Electron configurations tells you the quantum numbers of the
electron.
Energy sublevel

Principle quantum
number 1s2  two electrons
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• A matrix showing the
order in which the orbitals
are filled. Start at the top
left, then move from the
head of each arrow to the
tail of the one
immediately below it.
This sequence moves from
the lowest-energy level to
the next higher level for
each orbital.
27
valence electron are those that occupy the outermost shell.
they participate in the bonding between atoms to form
atomic and molecular aggregates. Furthermore, many of the
physical and chemical properties of solids are based on
these valence electrons.
example: C (atomic number = 6)
1s2 2s2 2p2

valence electrons

28
The periodic table
• All the elements have been classified according to
electron configuration.
• Elements are situated with increasing atomic number.
• Seven horizontal rows are called periods.
• All elements that are arrayed in a given column or group
have similar valence electron structures, as well as
chemical and physical properties.

29
Electropositive elements - capable of giving up their few valence electrons to become
positively charged ions.
Electronegative elements - readily accept electrons to form negatively charged ions, or
sometimes they share electrons with other atoms. 30
Atomic bonding in solids
Bonding forces and energies
• An understanding of many of the physical properties of materials is
predicated on a knowledge of the interatomic forces that bind the
atoms together.
• At large distances, the interactions are negligible, but as the atoms
approach, each exerts forces on the other. These forces are of two
types, attractive and repulsive, and the magnitude of each is a function
of the separation or interatomic distance.
• The origin of an attractive force FA depends on the particular type of
bonding that exists between the two atoms. The magnitude of the
attractive force varies with the distance. 31
• the outer electron shells of the two atoms begin to overlap, and a strong

repulsive force FR comes into play. The net force FN between the two
atoms is just the sum of both attractive and repulsive components; i.e.
FN = FA + FR

• When FA and FR balance, or become equal, there is no net force; i.e.

FA + FR = 0 , then a state of equilibrium exists. The centers of the

two atoms will remain separated by the equilibrium spacing r 0. For

many atoms, r0 is approximately 0.3 nm.

• Once in this position, the two atoms will counteract any attempt to
separate them by an attractive force, or to push them together by a
repulsive action. 32
(a) The dependence of
repulsive, attractive, and net
forces on interatomic
separation for two isolated
atoms.
(b) The dependence of
repulsive, attractive, and net
potential energies on
interatomic separation for two
isolated atoms.
33
Force-potential energy relationship for two atoms

EN = EA + ER

Here: A, B and n are “material constants” n is 7-9 for most ionic pairs
r r
EN  F

N dr   F

A  FR  dr

r
EA  F

A dr   A
r
where :
1
A  Z 1e   Z 2 e  -- Coulomb's Law
4 0
Z i is valence number of the species,
e is electronic charge,
 0 is the permittivity of a vacuum (8.85x1 0  12 F / m )

34
• Net bonding force curve for a Na+−Cl− pair showing an
equilibrium bond length of a0 = 0.28 nm.

35
Bonding energy, the curve shape, and bonding type
• Properties depend on shape, bonding type and values of curves: they
vary for different materials.
• Bonding energy (minimum on curve) is the energy that would be
required to separate the two atoms to an infinite separation.
• Modulus of elasticity depends on energy (force) versus distance
curve: the slope at r = r0 position on the curve will be quite steep for
very stiff materials, slopes are shallower for more flexible materials.

• Coefficient of thermal expansion depends on E0 versus r0 curve: a

deep and narrow trough correlates with a low coefficient of thermal
expansion
36
Primary interatomic bonds
• Ionic Bonding - Ionic Bonding is typical for elements that are
situated at the horizontal extremities of the periodic table.
• Atoms from the left (metals) are ready to give up their
valence electrons to the (non-metallic) atoms from the right
that are happy to get one or a few electrons to acquire stable
or noble gas electron configuration. As a result of this transfer
mutual ionization occurs: atom that gives up electron(s)
becomes positively charged ion (cation), atom that accepts
electron(s) becomes negatively charged ion (anion).
37
Formation of ionic bond:
1. Mutual ionization occurs by electron transfer
• Ion = charged atom
• Anion = negatively charged atom
• Cation = positively charged atom
2. Ions are attracted by strong coulombic interaction
• Oppositely charged atoms attract each other
• An ionic bond is non-directional (ions may be
attracted to one another in any direction) 38
Example : NaCl
• A strong electrostatic attraction between positively charged Na+
ions and negatively charged Cl- atoms along with Na+- Na+ and
Cl- - Cl- repulsion result in the NaCl crystal structure which is
arranged so that each sodium ion is surrounded by Cl- ions and
each Cl- ion is surrounded by Na+ ions.
• Any mechanical force that tries to disturb the electrical balance in
an ionic crystal meets strong resistance: ionic materials are strong
and brittle. In some special cases, however, significant plastic
deformation can be observed,
e.g. NaCl single crystals can be bent by hand in water. 39
• Ionic bonds: very strong, nondirectional bonds

40
• Attractive coulomb interaction between charges of
opposite sign:

• Repulsion due to the overlap of electron clouds at close

distances (Pauli principle of QM):

41
42
• Example: calculate the coulombic attraction between a pair of
Na+ and Cl- ions that just touch each other. Assume the ionic
radius of Na+ ion to be 0.095nm and that of Cl- ion to be
0.181nm.
W e seek FA (the force is a derivative of E A )

FA 
dE A

d A r  A

 Z 1e   Z 2 e 
dr dr r0 2
4  0  r0 2

 0.1602 x10   18 2


4  3.14159  8.854 x10    0.098  0.181  x10 
 12 9 2

 F A  com pute it
w here:
1
A  Z 1e   Z 2 e  w hich is C oulom b's Law
4  0
Here, ‘r0’ equals the sum of the ionic radii of each and represents
the r in the energy balance equations! 43
• Example 2 : if the attractive force between a pair of Mg+
and S- ion has a radius of 0.184nm, calculate the value
of ionic radius of Mg+ ion in nm.
We seek r0

FA  given 
 r   A   Z e  Z e
d A
1 2

dr r0 2
4 0  r0 2

1
A  Z1e  Z2e  -- Coulomb's Law
4 0
1
  Z1e   Z2e   2 10
 r0  (rS 2  rMg 2 )     2.489 x10 m
 4 0  FA 
and just solve for rMg 2 after plug & Chug  0.065 nm
44
Covalent Bonding
• In covalent bonding, electrons are shared between the
molecules, to saturate the valency. In this case the
electrons are not transferred as in the ionic bonding, but
they are localized between the neighboring ions and form
directional bond between them. The ions repel each other,
but are attracted to the electrons that spend most of the
time in between the ions.

45
Formation of covalent bonds:
• Cooperative sharing of valence electrons
• Can be described by orbital overlap
• Covalent bonds are HIGHLY directional
• Bonds - in the direction of the greatest orbital overlap
• Covalent bond model: an atom can covalently bond
with at most 8-N¹ , N¹ = number of valence electrons

46
Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5)

N¹ = 7, 8 - N¹ = 1 → can form only one covalent bond

Example: Carbon materials ZC = 6 (1S2 2S2 2P2)

N¹ = 4, 8 - N¹ = 4 → can form up to four covalent bonds
H H

ethylene molecule:
H H

47
polyethylene molecule:

ethylene mer

diamond: (each C atom

has four covalent
bonds with four other
carbon atoms)
48
• It is possible to have interatomic bonds that are partially ionic
and partially covalent, and, in fact, very few compounds exhibit
pure ionic or covalent bonding.
• For a compound, the degree of either bond type depends on the
relative positions of the constituent atoms in the periodic table.
• The wider the separation from the lower left to the upper-right-
hand corner (i.e., the greater the difference in electronegativity),
the more ionic the bond. Conversely, the closer the atoms are
together (i.e., the smaller the difference in electronegativity),
the greater the degree of covalency.
49
• The percentage ionic character of a bond between elements A
and B (A being the most electronegative) may be
approximated by the expression

% of ionic
={1-exp[-(1/4)(XA-XB)2]} X 100
character
where XA and XB are the electronegativities for the
respective elements.
Example: calculate the percentage ionic character of the
semiconducting compounds GaAs and ZnSe
electronegativity values (Ga = 1.6, As= 2.0, Zn= 1.6, Se= 2.4)
50
Metallic Bonding
• Metallic bonding, the primary bonding type, is found in metals
and their alloys.
• Metallic materials have one, two, or at most, three valence
electrons. 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 forming a “sea of electrons” or
an “electron cloud.”
• The remaining nonvalence electrons and atomic nuclei form what
are called ion cores, which possess a net positive charge equal in
magnitude to the total valence electron charge per atom. 51
• The free electrons shield the positively charged ion cores from
mutually repulsive electrostatic forces, which they would
otherwise exert upon one another; consequently the metallic
bond is nondirectional in character
Ion cores

In a metallic bonded
material, the valence
electrons are “shared”
among all of the ionic
cores in the structure
not just with nearest
neighbors!

Sea of valence electrons

Schematic illustration of metallic bonding.
52
• metals are good conductors of both electricity and heat, as a
consequence of their free electrons. By way of contrast, ionically
and covalently bonded materials are typically electrical and
thermal insulators, due to the absence of large numbers of free
electrons.
Secondary bonding (Van Der Waals bonding)
• Secondary, van der Waals, or physical bonds are weak in
comparison to the primary or chemical ones.
• 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. 53
• Secondary bonding is evidenced for the inert gases,
which have stable electron structures, and, in addition,
between molecules in molecular structures that are
covalently bonded.

Schematic illustration of van der

Waals bonding between two dipoles.

• The driving force for secondary bonding is the attraction

of the electric dipoles contained in atoms or molecules.
54
• An electric dipole moment is created when two equal and
opposite charges are separated. Electric dipoles are created
in atoms or molecules when positive and negative charge
centers exist.
+q -q

d
• Dipole moment- the charge value multiplied by the
separation distance between positive and negative charges
µ = qd
where: µ- dipole moment
q- magnitude of electric charge
d- separation distance between charge centers
55
 classification of Van Der Waals bonding
Instantaneous dipole - induced dipole interaction
• At any given instant in time the electron cloud will randomly
distorted, giving rise to a dipole of partial charges which then
induces a dipole in a neighboring molecule.
• The partial positive charge of one dipole will attract the partial
negative in the neighboring molecule or vice versa.

• The bigger the molecule, with more electrons in it, the more
polarizable it is in terms of dipole creation.
• Ex: the addition of every nonpolar -CH2- unit in the hydrocarbon
carbon chain produces a corresponding incremental rise in the
boiling point due to the incremental rise in intermolecular forces
(instantaneous dipole - induced dipole). 56
Permanent dipole - permanent dipole interactions
• If two atoms constituting a bond have significantly different
electronegativities, the bond will be permanently polar and produce
a permanently polar molecule.
• Such molecules posses dipole moment.
attractions seem to make little difference to the
bpt
Hydrogen bonding - Hydrogen bonds are a special type of dipole-
dipole attraction. The bonds between the hydrogen atom and
nitrogen, oxygen or fluorine are exceptionally short and polar.
Dipole-dipole attractions between these specific bonds are
particularly strong.

57
Permanent dipole - induced dipole interactions
• The permanently polar bond in one molecule can induce a
dipole in a neighboring molecule, whether the other
molecule is polar or non-polar.

Permanent dipole
Non-polar molecule
(polar molecule)

Permanent dipole Induced dipole in a non-polar molecule

(polar molecule)

Dipole-induced dipole interaction between permanent and induced dipole

58
Summary bonding
Type Bond Energy Comments

Ionic Large Non-directional (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

59
Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm

r Energy

• Bond energy, Eo
ro smaller Tm
Energy r

unstretched length
ro larger Tm
r
Eo = “bond energy” Tm is larger if Eo is larger.

60
Properties From Bonding : a

• Coefficient of thermal expansion, a

length, L o

unheated, T1
DL coeff. thermal expansion
heated, T2
DL
= a (T2 -T1)
• a ~ symmetry at ro Lo
Energy
unstretched length
ro a is larger if Eo is smaller.
r
Eo
smaller a

Eo larger a
61
Summary: Primary Bonds
Ceramics Large bond energy
(ionic and covalent bonding) large Tm
large E
small α
Metal Variable bond energy
Metallic bonding moderate Tm
moderate E
moderate α

Polymers Directional Properties

(covalent and secondary) Secondary bonding dominates
small Tm
small E
large α

62