Dr. Murad A.

AlDamen
Inorganic Chemistry 221
Inorganic Chemistry
Chemistry is like the story about the group of blind men who encountered an elephant? Each one
moved his hands over a different part of the elephant's body the trunk, an ear, or a leg and came up
with an entirely different description of the beast. In this elephant (chemistry), the part we see is
Inorganic Chemistry.
Fundamental particles of an atom
Atomic number, mass number and isotopes
Successes in early quantum theory
An introduction to wave mechanics
Atomic orbitals
Many-electron atoms
The periodic table
The aufbau principle
Ionization energies and electron affinities
Chapter 1: Basic Concepts: atoms
Chapter 1: Basic Concepts: atoms
An atom: the smallest unit quantity of an element that capable of existence
fm=femtometer
Fundamental Particles of an Atom
Protons
Found in nucleus
Relative charge of +1
Relative mass of 1.0073 amu
Neutrons
Found in nucleus
Neutral charge
Relative mass of 1.0087 amu
Electrons
Found in electron cloud
Relative charge of -1
Relative mass of 0.00055 amu
Relative atomic mass
The mass of a single atom is very small non integral number we define the
atomic mass 1/12 th of a
12
6
C atom, the atomic mass of
12
6
C=1.660x10
-27
kg,
1 amu (atomic mass unit)=1.660x10
-27
kg,
The mass on an atom=(the summation of protons)/(Avogadros number)
Atomic Number, Mass Number and Isotopes
Atomic number, Z
The number of protons in nucleus
The number of electrons in a neutral atom
The integer on the periodic table of each element
Mass Number, A
Integer representing the approximate mass of an atom equal to the sum of
the number of protons and neutrons in the nucleus=A-Z
Isotopes
Atoms of the same element which differ in the number of neutrons in the
nucleus designated by mass number
Some isotopes occur naturally others produce artificially,
Naturally elements (e.g.
31
15
P,
12
9
F) are monotopic naturally occurs with one isotope only.
With more than one isotope e.g.
12
C,
13
C and
14
C.
Isotopes can be separated by mass spectrometry.
Allotropes: Each of two or more different physical forms in which an element can exist.
Graphite, charcoal, diamond and fullerenes... are all allotropes of carbon (see page 384 for more information).
Caution! Do not confuse isotope and allotrope
E
A
Z
Element symbol
Successes in early quantum theory
Quantum theory: An introduction
Electrons in an atom occupy a region of space around the nucleus.
Understanding of the electronic structures leads to understand the properties of atoms, ions and molecules including
bonding and further interactions.
A way of understanding the electronic structures is through quantum theory and wave mechanics.
The quantum theory is necessary to describe electrons. It predicts discrete allowed energy levels and wavefunctions,
which give probability distributions for electrons. Wavefunctions for electrons in atoms are called atomic orbitals.
Although the electron is a wave and a particle at the same time, it easier and more convenient to consider the electron as
a particle rather than a wave.
We with Quantum Chemistry is like Alice
in marvel land.
Classical Quantum Mechanics
Observation!
At low temperatures, the radiation emitted by a hot body is mainly of low energy and occurs in the
infrared, but as the temperature increases, the radiation becomes successively dull red and white.
Explanation!
In the end of nineteenth century, much experimental work had been done on analysis this discrete spectrum
of radiation. attempts to explain this observation failed until, Planck suggested that energy could be
observed or emitted only in quanta of magnitude E related to the frequency of the radiation, .
E
E =constant*
E =h
c =
=c/
Wavelength ()
Speed of light (c)=2.998x10
8
m s
-1
Energy (E)
Frequency (v)
Plancks constant (h)=6.626x10
-34
J s
E =hc/
Planck relationship
wavenumber(v )=
1
wavelength(v)
cm
-1
Planck
Very precise spectroscopic measurements showed that hydrogen had the simplest spectrum of all the
elements. It was found that various lines in the optical and nonoptical regions where systematically spaced in
various series. Amazingly, it turned out that all the wavelengths of atomic hydrogen were given by a single
empirical relation Rydyberg formula.
where n
1
=1 and n
2
=2,3,4... gives the Lyman series (ultraviolet region)
where n
1
=2 and n
2
=3,4,5... gives the Balmer series (visible region)
where n
1
=3 and n
2
=4,5,6... gives the Paschen series (infrared region)
where n
1
=4 and n
2
=5,6,7... gives the Brackett series (far infrared region)
R
H
=1.097x10
7
m
-1
The existence of discrete spectroscopic frequencies is evidence that the
energy of the electron in the hydrogen atom is quantized. A photon
of light is emitted when the electron moves from a higher to a lower
energy level separated by energy difference, E=hv.
v =
1

= R
H
(
1
n
1
2

1
n
2
2
)
=
364.7n
2
n
2
4
(n = 3, 4, 5...)
Balmers equation
Experimentally!
Bohrs equation
R. Grinter, THE QUANTUM IN CHEMISTRY: An Experimentalists View, , John Wiley &
Sons Ltd, 2005.
1. The electron in the hydrogen atom orbits the nucleus in a circular path, like a planet around the sun.
2. Of the infinite number of possible orbits, only those are allowed for which the orbital angular
momentum (mvr) of the electron is an integral multiple of Plancks constant divided by 2 .
3. Contrary to classical electromagnetic theory, electrons in these allowed orbits do not radiate energy.
4. When an electron changes its orbit a quantum of energy (photon) is emitted or absorbed in accordance
with the equation h, where is the difference in the energy of the two orbits.
Bohrs Laws of the Hydrogen Atom Structure
v
+e
M
-e m
e
from eq.2 and eq.3 we obtain
E=potential energy+kinetic energy
E= e
2
/(4
0
v
2
)+m
e
v
2
/2 by eq.1 and eq.2 and after some algebraic rearrangements:
=-e
2
/(4
0
) (e
2
m
e
)/(
0
n
2
h
2
) +m
e
/2(e
2
/(2
0
nh))
2
=(-e
4
m
e
)/(8
0
2
n
2
h
2
)
E(n)=-1/n
2
(e
4
m)/(8
0
2
h
2
)
Bohrs 1st law: The electron in the hydrogen atom orbits the nucleus in a circular path, like a
planet around the sun.
The electron does not fall into the nucleus because of its velocity at right-angles to the line between
the two particles. the radial vector.
The coulombic force does cause an acceleration of the electron towards the nucleus equal to -v
2
/r.
According to Newton, force=mass x acceleration so: e
2
/(4
0
r
2
)=m
e
v
2
/r r= e
2
/(4
0
v
2
) ....eq.1
Bohrs 2nd law: This law introduces quantization with the postulate that only those orbits for
which the angular momentum is an integer multiple of h/2 are allowed,
i.e. the angular momentum=nh/2 or m
e
vr=nh/2 where n=1,2,3..., ...eq.2
to eliminate the v we use from eq.1. r= e
2
/(4
0
v
2
)= or r=e
2
/(4
0
) 1/v
2
and from eq 2.
v=nh/(2m
e
r) 1/v
2
=(2m
e
r)
2
/(nh)
2
then m
e
r=(
0
n
2
h
2
)/(e
2
) .....eq.3
v=nh/(2m
e
r)=nh/2 e
2
/(
0
n
2
h
2
)= e
2
/(2
0
nh)
E(n)=hv=hc/
Bohrs equation
Amazingly, when a viable theory was found, two apparently very different theories were announced
at almost the same time. Karl Werner Heisenberg described his matrix mechanics in 1925 and Erwin
Schrdinger his wave mechanics in 1926. But the two approaches were soon shown to be different
formulations of the same theory (compare the Newtonian, Lagrangian and Hamiltonian forms of
classical mechanics), and we shall deal only with Schrdingers version here.
de Broglie (1892 1987) descended from a noble family who had served many French kings.
He studied history before taking up physics and in his doctoral dissertation (1924) he reasoned as follows:
According to Einsteins theory of relativity:
E=mc
2
but Einstein, following Planck also suggested that:
E=hv=hc/
therefore, if the momentum (p) of the photon as a particle is mc, then:
p = mc = E/c = h/
and if this result applies to other particles as well as to photons, then all moving particles
should be associated with a wavelength () given by the equation:
= h/p = h/mv
where m and v are the mass and velocity of the particle respectively.
The wave-nature of electrons
E
i
n
s
t
e
i
n

l
i
v
e
d

h
e
r
e
The uncertainty principle
Electrons moving in circles around the nucleus, as in Bohr's theory, can
be thought of as forming standing waves that can be described by the de
Broglie equation. However, we no longer believe that it is possible to
describe the motion of an electron in an atom so precisely. This is a
consequence of another fundamental principle of modern physics,
Heisenberg's uncertainty principle, which states that there is a
relationship
ApAx >
h
4t
x = uncertainty in the position of the electron
p
x
= uncertainty in the momentum of the electron
This concept means that we cannot treat electrons as simple particles
with their motion described precisely, but we must instead consider the
wave properties of electrons, characterized by a degree of uncertainty in
their location. In other words, instead of being able to describe precise
orbits of electrons, as in the Bohr theory, we can only describe orbitals,
regions that describe the probable location of electrons. The probability
of finding the electron at a particular point in space (also called the
electron density) can be calculated, at least in principle.
The probability of finding an electron at a given point in space is
determined from the function
2
where is the wavefunction
Imagine a car in a circle, when this ball has zero velocity
then its momentum will be zero, and so we can
determine where is the ball exactly. If this ball moves by
very high speed, then we will see the car in all the circle,
it means that our accuracy in determining the position of
the car will decreases and the energy increases.
v=0
p=0
v=v
0
p=mv
0
The Schrdinger equation describes the wave properties of an electron in terms of its position, mass, total
energy, and potential energy. The equation is based on the wave function, , which describes an electron
wave in space; in other words, it describes an atomic orbital. In its simplest notation, the equation is:
The Schrdinger wave equation
H=E
H=The Hamiltonian operator
= The wave function
E= The energy of the electron
H =
h
2
8t
2
m
(
c
2
cx
2
) +V In the form used for calculating energy levels, the Hamiltonian operator is
The image above is not of an atom, but shows an alternative
electron corral pattern, predicted by the Schrdinger wave
equation and created by electrons in experiment
This equation can exactly be solved only for hydrogen-like atom: An
atom contains a nucleus and only one electron
Courtesy D. Eigler, IBM research division
Particle in a Box
1. The wave function is a solution of the Schrdinger equation and describes the
behavior of an electron in a region of space called atomic orbital.
2. We can find the energy values that are associated with particular wave functions.
3. The quantization of energy levels arises naturally from the Schrdinger equation.
c
2

cx
2
+
8t
2
m
h
2
(E V) = 0
=Asin(rx)+Bcos(sx) substitution into Schrdinger equation leads: r=s=(2mE) 2/h
ra=n or r=n/a=(2mE) 2/h
E=n
2
h
2
/(8ma
2
)
The wave function =(2/a) sin (nx/a)
where n: principal quantum number
A number of conditions required for a physically realistic solution for in atoms:
1. The wave function must be single valued.
2. The wave function and its derivatives must be continuous.
3. The wave function must be quadratically integrable. This means that *.d=1. This
is called normalizing the wave function.
4. Any two solutions to the wave function must be orthogonal, which means
A

B
.d=0
see Box 1.3
V=
V=0
V=
Potential Energy Node Node
x=rsin \
y=rsin \ sin |
z=rcos \
dx.dy.dz=r
2
sin(\).d\.d|.dr
(r,\,|)=R(r)(\)(|)
radial factor angular factors
Atomic Orbitals
The wavefunctions of the hydrogen atom are not easy to describe in a Cartesian co- ordinate system of three, mutually
perpendicular axes. The polar co-ordinate system with the nucleus at the origin is much more suitable. The mathematical functions
for atomic orbitals may be written as a product of two factors:
The radial wavefunction describes the behavior of the electron as a function of distance from the nucleus; the angular wavefunction
shows how it varies with the direction in space. (Describe the electron density)
Angular wavefunctions do not depend on n and are characteristic features of s, p, d,...orbitals. (Describe the shape and orientation)
Quantum numbers and their properties
Symbol Symbol
Name Name Values Values Role Role
n
Principal 1,2,3,... Determine the size and so the major part of energy
l
Angular momentum 0,1,2,3,...n-1 Describes angular dependence (shape) and contributes to the energy
m
l
Magnetic
0,1,2,3,..
.l
Describes orientation in space
m
s
Spin Describes orientation of the electron spin in space
Orbitals with different l values are usually known by the following labels, which are derived from early terms for different
families of spectroscopic lines:
l=
label
0 1 2 3 4 5, ...
s, p, d, f, g, continuing alphabetically
For a given value of n (n1) there is one s atomic orbital
For a given value of n (n2) there are three degenerate p atomic orbitals
For a given value of n (n3) there are five degenerate d atomic orbitals
For a given value of n (n4) there are seven degenerate f atomic orbitals
s sharp, p principal, d diffuse, f fundamental
+
-
2
1 3p
4p nodes
node
+
-
n-1 Total
n-l-1 Radial
l Angular
Radial wavefunctions depend on n and l but not on m; thus each of the three 2p orbitals has the same radial form. The
wavefunctions may have positive or negative regions, but it is more instructive to look at how the radial probability distributions for
the electron depend on the distance from the nucleus.
Radial distributions may have several peaks, the number being equal to n-1.
The outermost peak is by far the largest, showing where the electron is most likely to be found.
The distance of this peak from the nucleus is a measure of the radius of the orbital, and is roughly
proportional to n
2
(although it depends slightly on l also).
Radial distributions determine the energy of an electron in an atom. As the average distance from the
nucleus increases, an electron becomes less tightly bound. The subsidiary maxima at smaller distances
are not significant in hydrogen, but are important in understanding the energies in many-electron
atoms.
Radial Part
Radial Distribution Function
1 atomic unit=Bohrs radius=5.293pm
Probability of finding the electron at r = 4r
2
R
2
Example
Nodal Planes
d
xy
The five degenerate d orbitals
Angular Part
Orbital sign key
0 1 2 3 4 5 6
1 2 3 4 5 6
Total number of nodes=n-1
s
p
z
2 3 4 5 6
2 3 4 5 6
d
z2
d
xz
nodes
nodes
nodes
nodes
n=1
l=0
m=0
n=2 n=3 n=4 n=5 n=6 n=7
l=1
m=0
l=2
m=0
l=2
m=1
Orbital angular momentum=
h
2t
l(l +1)
Spin angular momentum=
h
2t
s(s +1)
Example:
l=2, m
l
=-2,-1,0,+1,+2
Orbital angular momentum=
Actual magnitude of z component of l=
m
l
h
2t
h
2t
6
Total angular momentum=
h
2t
j( j +1)
Actual magnitude of z component of s=
m
s
h
2t
j = l +
1
2
or l
1
2
l=0 no angular momentum
Total angular momentum=
h
2t
8.75 or
h
2t
3.75
j possible orientations
Angular momentum, the inner quantum number, j, and spin-orbit coupling
R = Rydberg constant=1.097 10
7
m
-1
h = Planck constant=6.626 10
-34
J s
c= Speed of light=3.000 10
8
m s
-1
Z is the atomic number
Hydrogen-like
Hydrogen1ssphericalonly depends on n (l doesn't affect the energy)
E
n
=
RhcZ
2
n
2
r =
n
2
a
0
Z
3s
2s
1s
2p
3p 3d 3d 3d 3d
3s
3s
3s
2s
2s
2s
1s
1s
1s
3p
3p
3p
2p
2p
2p
E
n
e
r
g
y

(
n
o
t

t
o

s
c
a
l
e

Three multielectron atoms Hydrogen atom

Li (Z=3) Na (Z=11) K (Z=19)
The aufbau Principle
1- Orbitals are filled in order of energy
2- Hunds rule of maximum multiplicity: electrons be placed in orbitals so as to give the maximum total spin possible.
3- Pauli exclusion principle: each electron in an atom have a unique set of quantum numbers.
degenerate for Hydrogen atoms
degenerate for Hydrogen atoms
1s
2s
3s
4s
5s
6s
7s
2p
3p
4p
5p
6p
7p
3d
4d
5d
6d
4f
5f
First Rule
adding to 3d (4s
1
3d
n
)
adding to 4f (4f
n
6d
2
)
adding to 4f (4f
n
6s
2
5d
1
)
adding to 6d (6d
n
7s
2
)
adding to 5f (5f
n
7s
2
6d
1
)
adding to 3d (5s
0
3d
10
)
adding to 4d (5s
1
4d
n
)
adding to 5f (5f
n
7s
2
)
A
l
k
a
l
i

m
e
t
a
l
s
A
l
k
a
l
i

e
a
r
t
h

m
e
t
a
l
s
d-block elements
P
n
i
c
t
o
g
e
n
s
C
h
a
l
c
o
g
e
n
s
H
a
l
o
g
e
n
s
N
o
b
l
e

g
a
s
e
s
Hunds Rule
Step 1 Step 2 Step 3

e
total pairing energy==
c
+
e
Oxygen
Or
=3
e
+
c
=2
c
+2
e

e
add stability
c
add instability
When two electrons (e.g. Helium atom) occupy the same part of the space around an atom, they repel each other because of their
mutual negative charges, with a Coulombic energy of repulsion,
c
.
In addition, there is an exchange energy,
e
, which arises from purely quantum mechanical considerations; the number of
electrons at the same energy that could be exchanged while retaining the same overall spins.
see Box 1.8
In this atom, the electrons of 1s are the core electrons (lower energy quantum levels)
and those of 2s, 2p are valence electrons (outer)
2s and 2p ...etc penetrate the 1s
2s more penetrating than 2p
The core electrons shield the valence electrons from the nuclear charge, i.e. 1s shield the
nucleus and the atomic number will replace with effective charge Z
eff
Z
eff
can be calculated by Slaters rules, which is based on experimental data.
Effective charge(Z*)=number of protons(Z)-Shielding(S)
1. The electronic structure of the atom is written in groupings as follows: (1s) (2s, 2p) (3s,
3p) (3d) (4s, 4p) (4d, 4f) (5s, 5p), etc.
2. Electrons in higher groups (to the right in list above) don not shield those in lower groups.
3. For ns or np valence electrons:
a. Electrons in the same ns, np group contribute 0.35, except the 1s, where 0.30 works better.
b. Electrons in the n-1 group contribute 0.85.
c. Electrons in the n-2 or lower groups contribute 1.00.
4. For nd and nf valence electrons:
a. Electrons in the same nd or nf group contribute 0.35.
b. Electrons in groups to the left contribute 1.00.
At maximum 1s, 2s>2p, and
so the electron will insert in
the orbital that is closer to
the nucleus.
Oxygen (1s
2
) (2s
2
p
4
) Z=8
For outmost electron Z*=Z-S=
8-2*0.85-5*0.35=4.55
Z (1s) (2s,2p)
4.55/8*100%=57% force expected for 8
nucleus and -1 electron
Shielding (S) (Screening)
Ionization energy The general increases in IE
1
across a given period is a consequence of an increase
in Z
eff
. A group 15 element has a ground state electronic configuration ns
2
np
3
and the np level is half-
occupied. A certain stability is associated with such configurations and it is more difficult to ionize a group
15 element than its group 16 neighbor. In going from Be (group 2) to B (group 13), there is a marked decrease
in IE
1
and this may be attributed to the relative stability of the filed shell 2s
2
configuration compared with the
2s
2
2p
1
arrangement; similarly, in going from Zn (group 12) to Ga (group 13), we need to consider the
difference between 4s
2
3d
10
and 4s
2
3d
10
4p
1
configurations.
Electron Affinity The attachment of an electron to an atom is usually exothermic. Two electrostatic
forces oppose one another: the repulsion between the valence shell electrons and the additional electron, and
the attraction between the nucleus and the incoming electron. In contrast, repulsive interactions are dominant
when an electron is added to an anion and the process is endothermic.
A(g) +e
-
A

(g)
Electron affinity=EA=-U
A
n+
(g) A
(n+1)+
(g) +e
-
Ionization energy=U
Ionization energy and Energy Affinity
Ion Protons Electrons Radius(pm)
O
2-
8 10 126
F
-
9 10 119
Na
+
11 10 116
Mg
2+
12 10 86
Ion Protons Electrons Radius(pm)
O
2-
8 10 126
S
2-
16 18 170
Se
2-
34 36 184
Te
2-
52 54 207
Ion Protons Electrons Radius(pm)
Ti
2+
22 20 100
Ti
2+
22 19 81
Ti
2+
22 18 75
+
+
+
-
- -
-
+
+
+
-
- - +
Atomic and Ionic Radii Trends
Orbital is like ghost, we cannot see it but some
believe that it exists
Atomic units
Conclusions and Appendices
Bonding model
Homonuclear diatomic molecules
The octet rule isoelectronic species
Molecular shape and the VSEPR model
Molecular shape: Stereoisomerism
Electronegativity values
Dipole moments
Chapter 2: Basic Concepts: molecules
A cartoon rendition of Irving Langmuir and G.N. Lewis ;
Source: http://www.minerva.unito.it/humor/Langmuir%20&%20Lewis.htm
Lewis, Kossel, and Langmuir made several important proposals on bonding which lead to the development of Lewis
Bonding Theory
Elements of the theory:
Valence electrons play a fundamental role in chemical bonding.
Ionic bonding involves the transfer of one or more electrons from one atom to another.
Covalent bonding involves sharing electrons between atoms.
Electrons are transferred or shared such that each atom gains an electron configuration of a noble gas
(ns
2
np
6
), i.e. having 8 outer shell (valence) electrons.
This arrangement is called the octet rule.
Exceptions to the octet rule do exist and will be explored later.
Lewis Bonding Theory
Lewis Symbols represent the resulting structures that accommodate the octet rule.
In a Lewis symbol, an element is surrounded by up to 8 dots, where elemental symbol represents
the nucleus and the dots represent the valence electrons.
1A(1)
ns
1
2A(2)
ns
2
3A(13)
ns
2
np
1
4A(14)
ns
2
np
2
5A(15)
ns
2
np
3
6A(16)
ns
2
np
4
7A(17)
ns
2
np
5
8A(18)
ns
2
np
6
Li
Be
B
Na Mg Al
C
Si
N O F Ne
P S
Cl
Ar
2
3
Octet Rule
Ionic bond: e.g.
Na

Na
-
+

+
Cl
Cl
-
Cl
-
Na
+
metal nonmetal
small ion large ion Loss Gain
Covalent bond: e.g.
Cl
Share
Cl Cl Cl

nonmetal nonmetal
O
H
H

Lewis formula
O
H
H
Kekul formula

How can we write Mg

3
N
2
???
Homonuclear covalent bond
Homonuclear molecule
Homonuclear covalent bond
Homonuclear molecule
Homonuclear covalent bond
Heteronuclear molecule
Homonuclear covalent bond
Heteronuclear molecule
H

H

H

H

2
C

F
F
F
F
+
+
+
+
Covalent Bond
Unequally shared: polar covalent bond
Bond order: Single, Double, Triple, Quadruple, Quintuple, Sextuple
Single e.g.
Cl
Share
Cl
Cl Cl

O
H
H
Share

O
H
H
Equally shared: nonpolar covalent bond

Double e.g. O O

Triple e.g.
N N

Quadruple e.g.
Cl
4
Re ReCl
4

Quintuple e.g.
RCr
CrR

;R=large organic group

Sextuple e.g.
W
W

Zeruple e.g.
The carbon atom in C(PPh
3
)
2
(where Ph stands for a benzene ring) has
two lone pair electrons, but no electrons connected to the bonded groups
2005 Philip Power, U of California, Davis
1964 F. Albert Cotton, Texas A&M University
2006 (Roos, Gagliardi, Borin, U of So Paulo)
Xe 3+
O 1-
Expanded Shells
1. Elements in the third or higher shells can have >8 valence electrons
2. Empty d-orbitals are used to hold excess electrons (s
2
p
6
d
10
=18 electrons max)
S
N
F F
F
S
O
Cl O
Cl
Xe
O
O O
S
O
O O
O
S
O
O O
S
N
F F
F
S
O
Cl O
Cl
S
O
O O
O
S
O
O O
I
O
F
F F
F
F
I
O
F
F F
F
F

Xe
O
O O

S 2+
N 2-
S 2+
O 1-
S 2+
O 1-
S 1+
O 1-
S 0
N 0
S 0
O 0
Xe 0
O 0
S 0
O 0,1-
S 0
O 0,1-
O 1+
I 1-
O 0
I 0
Anion Formal Charge Anion Formal Charge Molecule Expanded to
SNF
3
SO
2
Cl
2
XeO
3
SO
4
2-
SO
3
2-
IOF
5
No octet rule
12
12
14
12
10
12 or 14 Or
Decreasing the formal charge
No octet mean, it is not possible to draw the molecule with 8 electrons around the central atom
Resonance and Formal Charge
1. Ability to draw multiple Lewis structures for the same molecule
S
O
O
O
S
O
O O
S
O
O
O
a. Taken as a set to represent the true structures
b. Interconverted by movement of e
-
only
c. Separated by double headed arrows
More resonance structures means a lower energy for the compound; Spreading the electrons overe more
atoms lets them occypy more space.
Isoelectronic=resonance structures with identical electronic structures
a) SO
3
and CO
3
2-
Resonance structures may be electronically different as well amides
C H
3
C
O
NH
2 C H
3
C
O
NH
2
distance in pm S-C C-N
SCN
-
165 117
HSCN 156 122
Single bond 181 147
double bond 155 ~128
triple bond 116
Data from A. F. Wells, structural Inorganic Chemistry, 5th ed. OXford University Press, New York,
1984, pp. 807, 926, 933-934
distance in pm O-C C-N
OCN
-
113 121
HNCO 118 120
Single bond 143 147
double bond 116 ~128
triple bond 113 116
Thiocyanate SCN
-
Cyanate OCN
-
Fluminate CNO
-
S=C=N SCN SCN
O=C=N OCN OCN
C=N=O CNO CNO
1- 1- 2- 1+
1- 1- 2- 1+
2-
1+ 1+ 1+ 3- 1+ 1+ 1-
Formal charge=valence electrons in Neutral atom-(unshared valence
electrons+half os shared electrons)
Could not explain:
a. Why metals conduct electricity
b. How a semiconductor works
c. Why liquid oxygen is attracted into the magnetic field of a large magnet
d. Be and B compounds
1. BeX
2
and BX
3
compounds have <8 electrons around Be/B if single bonds
2. Be/B=X double bonds create large charge separation
3. Solids tend to have extended structures relieving charge separation/octet
4. Monomers are reactive as Lewis acids (electron pair acceptors), even though the
small atom size allow less than an octet around Be/B
Shortcomings of Lewis theory
Be
F
F F
F
Be
Be
F
F
F
F
F
F
Be F F Be F F
B F
F
F
B F
F
F
B F
F
F
B F
F
F
Predicted: The B-F bond length is 131 pm the calculated single-bond length is 152 pm
Predicted
Actual salt
Valence Shell Electron Pair Repulsion Theory
1. All paires of electrons, both bonding pairs and lone pairs, are important in determining the shape of a
molecule.
2. Bonding pairs are smaller than lone pairs because there are 2 positively charged nuclei pulling them in.
3. Single bonds are smaller than double bonds and double bonds are smaller than triple bonds.
4. If a central atom (A) is surrounded by different atoms (B and C) in the molecule AB
x
C
y
, the relative sizes
of B and C can affect the structure of the molecule.
Determine the ValenceDetermine the valencyDraw LewisCount the lone pairs
The true bond angles will usually be distorted from the idealized angles in the pictures above because
all bonds and non-bonding electron pairs don't have the same "size".
lone pairs > triple bond > double bond > single bond
Valence Shell Electron Pair Repulsion Theory:
Coordination Geometry
AX
2
Linear
BeCl
2
, CO
2
, HCN
AX
3
Trigonal planar
SO
3
, BeCl
3
AX
2
E
Bent
O
3
, SnCl
2
AX
4
AX
5
Valence Shell Electron Pair Repulsion Theory:
Coordination Geometry
AX
3
E AX
2
E
2
Tetrahedral Trigonal pyramidal Bent
SO
4 ,
POCl
3 ,
SiF
4
(H
3
O)
+
,
NH
3 ,
PCl
3
H
2
O , Cl
2
O, (NH
2
)
-
AX
4
E AX
3
E
2
AX
2
E
3
Trigonal bipyramidal Seesaw T-shaped Linear
SOF
4
, PCl
5
XeO
2
, IF
2
O
2
, SiF
4
ClF
3
I
3
-
AX
7
AX
8
AX
6
Valence Shell Electron Pair Repulsion Theory:
Coordination Geometry
AX
5
E AX
4
E
2
AX
3
E
3
Octahedral Square pyramidal Square planar T-shaped
IOF
5
, SF
6
XeOF
4
, BrF
5
ICl
4
-
[Ln(H
2
O)
8
]
3+
Square antiprismatic trigonal bipyramidal
Valence Shell Electron Pair Repulsion Theory:
Second order effects
Influence of the nature of electron pairs on the angles between bonds
It's logical to admit that the non-bonding pairs, less confined in the internuclear space than bonding pairs, occupy a
higher volume. And so, we see a diminution of the angles between the bonds when we observe in the order CH
4
, NH
3
and H
2
O.
109.5 107 104.5
[NH
4
]
+
NH
3
[NH
2
]
-
Influence of the volume of the multiple bonds
The geometric form depends only on o bond. So we can class the molecules with t bonds in the same groups that
these with only o bonds. But the volume occupied by the electrons depends on the number of t bonds, and then we
observe a diminution of the opposite angle of the t bond.
109.5 102 98
SiF
4
POF
3
NSF
3
Isomerism
equatorial axial
Bond Polarity
.
0 0.4 2.0 4.0
Electronegativity Difference
covalent ionic
polar
non
polar
3.0-3.0
= 0.0
4.0-2.1
= 1.9
3.0-0.9
= 2.1
Pauling electronegativity values
P
bond enthalpy=D(XY)=(D(XX)+D(YY))
=
P
(Y)-
P
(X)=D
Mulliken electronegativity values
M

M
=(Ionization energy+Electron affinity) eV
Allerd-Rochow electronegativity values
AR

AR
=(3590xZ
eff
/r
cov
2
)+0.744; r
cov
in pm
Eleectronegativity difference
The symmetrical electron distribution in the bond of a homonuclear diatomic renders the bond non-polar. In a heteronuclear
diatomic, the electron withdrawing powers of the two atoms may be different, and the bonding electrons are drawn closer
towards the more electronegative atom. The bond is polar and possesses an electric dipole moment ()
=ed
e charge of the electron, d bond distance electric dipole moment
point charge
Measure of the pull an atom has on bonding electrons
Increases across period (left to right) highest at F
Decreases down group (top to bottom)
Large difference in electronegativity, more polar the bond
Negative end toward more electronegative atom
System operations and symmetry elements
Successive operations
Point groups
Introduction to character tables
An introduction to Molecular Symmetry Chapter 4
Symmetry operations are geometrical operations applied to molecules (or better, molecular models). The
application of a symmetry operation to a particular molecular geometry produces a spatial orientation which
is indistinguishable from the initial orientation.
The five basic symmetry operations that need to be considered are identity, rotation, reflection (mirroring),
inversion, and rotary reflection.
For each symmetry operation there is a corresponding symmetry element, with respect to which the
symmetry operation is applied. For example, the rotation (a symmetry operation) is carried out around an
axis which is the corresponding symmetry element. Other symmetry elements are planes (for reflections)
and points (for inversions).
Different (valid) combinations of symmetry operations that leave at least a single common point (the
molecular center) unchanged give rise to the so called point groups (not all arbitrary combinations of
symmetry operations and elements are possible, and some combinations of symmetry operations implicitly
imply others, see below).
Symmetry
The basic symmetry operations are:
Identity Operation E The identity operation does nothing and leaves any molecule unchanged, the corresponding symmetry element is
the entire object (molecule) itself. The reason for including this symmetry operation is that some molecules have only this symmetry
element and no other symmetry properties. Another reason is the logical completeness of the mathematical description of group theory.
Inversion i The inversion (the symmetry operation) through a center of inversion (the symmetry element, which must be identical to the
center of geometry of the molecule) takes any point in the molecule, moves its to the center, and then moves it out the same distance on
the other side again (sometimes called point reflection). The benzene molecule, a cube, and spheres do have a center of inversion,
whereas a tetrahedron does not.
Reflection The reflection (the symmetry operation) in a plane of symmetry or mirror plane (the corresponding symmetry element)
produces a mirror image geometry of the molecule. The mirror plane bisects the molecule and must include its center of geometry. If this
plane is parallel to the principal axis (and includes it, see below), it is called a vertical mirror plane denoted
v
, if it is perpendicular to the
principal axis (and bisects it in the molecular center of geometry), it is denoted a horizontal mirror plane
h
. Vertical mirror planes
bisecting the angle between two Cn axes are called dihedral mirror planes
d
(these mirror planes all include principal axis and intersect in
it).
n-Fold Rotation Cn The n-fold rotation (the symmetry operation) about a n-fold axis of symmetry (the corresponding symmetry element)
produces molecular orientations indistinguishable from the initial for each rotation of 360/n (clockwise and counter-clockwise). A water
molecule has a single C
2
axis bisecting the H-O-H bond angle, and benzene has one C
6
axis (amongst one C
3
axis and seven C
2
axes of
which the C
3
and one C
2
axis coincide with the C
6
axis). Linear molecules display a C

axis (any infinitely small rotation about this axis
produces unchanged orientations), and perfect spheres posses an infinite number of symmetry axes along any diameter with all possible
integral values of n. If a molecule has one (or more) rotation axes Cn or Sn (see below), the axis with the greatest n is called the
principal axis.
n-Fold Rotary Reflection Sn The n-fold rotary reflection (or n-fold improper rotation, the symmetry operation) about an n-fold rotary
reflection axis (or n-fold axis of improper rotation) is composed of two successive geometry transformations: first, a rotation through
360/n about the axis of that rotation, and second, reflection through a plane perpendicular (and through the molecular center of
geometry) to that axis. Neither of these two operations (rotation or reflection) alone is a valid symmetry operation, but only the outcome
of the combination of both transformations.

C
6
C
6
S
6

C
2

C
6

v
C
2
C
2

v
C
2

h
Between two C
2
Parallel to the principal
rotation axes (
v
)
Perpendicular to principal
rotation axes (
h
)
Mirror plane ()
Identity (E) Inversion (i)
n-fold rotation axis (C
n
) n-fold improper axis (S
n
)
The basic symmetry operations are:
Symmetry operations examples:
only E
i

C
2
C
3
S
4
S
1
=
S
2
= i
For this reason, if the molecule
has S
1
or S
2
, we use and i.
Chiral?
All molecules (or molecular conformations)
belonging to the C
1
, Cn, Dn, or the (very
rare) T, O, or I point groups MUST be chiral.
All other point groups include symmetry
elements that (any Sn axis, including mirror
planes = S
1
or inversion centers i = S
2
)
require a molecular geometry to be
superimposable to its mirror image
geometry, and therefore these molecules
MUST be achiral
Polar molecules must have a permanent
electric dipole moment. Only molecules
belonging to the point groups Cn (including
C
1
), Cn
v
, and C
s
, may have a permanent
dipole moment, which in the case of Cn and
Cn
v
must lie along the rotation axis. All other
point groups posses symmetry operations
that include Cn axes (n > 1, and thus no
dipole moment perpendicular to these axes),
and symmetry operations which take one
end of the molecule into the other (therefore
no dipole moment along the principal axis
can be observed).
Permanent electrical dipole moment?
cont.
EXAMPLES
cont.
EXAMPLES
cont.
C
v
EXAMPLES
cont.
D
h
EXAMPLES
cont.
EXAMPLES
EXAMPLES
Chemists and physicists use a special convention for representing character tables which is applied
especially to the so-called point groups, which are the 32 finite symmetry groups possible in a
lattice. In the following example:
Character Table
1. The symbol used to represent the group in question (in this case C
3v
).
2. The conjugacy classes, indicated by number and symbol, where the sum of the coefficients gives the
group order of the group.
3. Mulliken symbols, one for each irreducible representation.
4. An array of the group characters of the irreducible representation of the group, with one column for
each conjugacy class, and one row for each irreducible representation.
5. Combinations of the symbols x, y, z, R
x
, R
y
and R
z
the first three of which represent the coordinates
x,y and z and the last three of which stand for rotations about these axes. These are related to
transformation properties and basis representations of the group.
6. All square and binary products of coordinates according to their transformation properties.
3. Mulliken Symbols
The character tables contain various information, for instance the number and kind of irreducible
representations for a specific point group. Usually these irreducible representations are denoted using a
scheme suggested by Robert S. Mulliken (1896-1986, awarded with the Nobel prize in 1966) in the
early 1930s. Here, an overview on the meaning of Mulliken's symbols is given.
1. The dimension of characters are denoted with one of the following capital letters:
dimension Mulliken symbol
1 A and B
2 E
3 T
threefold degeneracy
twofold degeneracy
not degenerated
one electron system
a and b
e
t
2. If C
n
represents rotation about the principal axis, the one-dimensional characters are denoted dependent of the
value obtained for (C
n
).
(C
n
) denoted as
+1 A
-1 B
cont.
symmetric
antisymmetric
3. Mulliken Symbols
3. Indices reflect an additional classification of symmetry. If the molecule possesses an axis C
2
or a plane of reflection
or
d
perpendicular to the principal axis C
n
, the values for function change or keep their sign and are therefore
regarded as symmetric and antisymmetric respectively.
function Index
Sign unaffected 1
Change sign 2
4. Dependent on the effect of inversion i, Mulliken's symbols take the indices g for gerade and u for ungerade.
5. The way reflection on a horizontal plane affects a function is denoted by primed or doubly primed symbols.
(i) Index
Sign unaffected g
Change sign u
(
h
) Index
Sign unaffected
Change sign
4. Orbital symmetry (C
2v
as an example)
(E) (C
2(z)
) (
v(xz)
) (
v(yz)
)
z
x
y
p
z
z
x
y
p
y
+1 +1 +1 +1
+1 -1 -1 +1
x
y
p
x
+1 -1 +1 -1
z
4. Translational motion
z
y
x
O
H H
(E)
(C
2(z)
)
(
v(xz)
) (
v(yz)
)
+1 -1 -1 +1
doesnt translate translate translate doesnt translate
H translation:
+1 +1 -1 -1
doesnt rotate rotate rotate H rotation along z : doesnt translate
Infrared (IR) active vibrations
IR : one dimensional
Raman: two dimensional
There are two types of spectroscopy that involve vibrational transitions. infrared
spectroscopy. During infrared spectroscopy experiments we observe transitions between
vibrational energy levels of a molecule induced by the absorption of infrared (IR) radiation.
The second type of vibrational spectroscopy is Raman spectroscopy. In Raman
spectroscopy, vibrational transitions occur during the scattering of light by molecules.
At room temperature almost all molecules are in their lowest vibrational energy levels with
quantum number n = 0. For each normal mode, the most probable vibrational transition is
from this level to the next highest level (n = 0 -> 1). The strong IR or Raman bands resulting
from these transitiions are called fundamental bands. Other transitions to higher excited
states (n = 0 -> 2, for instance) result in overtone bands. Overtone bands are much weaker
than fundamental bands
Valence bond (VB) theory: hybridization of atomic orbitals
Valence bond (VB) theory: multiple bonding in polyatomic molecules
Chapter 5 - Part 1
Valence Bond Theory and Hybrid Orbitals
The Linear Combination of Atomic Orbitals (LCAO) is a mathematical method to construct a new set of orbitals - the
hybrid orbitals - by mixing appropriate atomic orbitals (AOs)
Valence bond theory describes a chemical bond as the overlap of atomic orbitals.
repulsion occurs
some overlap attraction begins
maximum overlap attraction begins
Potential Energy
r
74 pm
-436 kJ/mol
0
H+HH:H

i
= c
i,1

1
+ c
i,2

2
+... + c
i,n

n
Orthogonality c
i, j
2
j

=1 and c
i, j
c
k, j
j =k

= 0
2sp-orbitals
e.g. BeH
2
Be
1s 2s 2p
1s 2s 2p
1s 2sp 2p
Be
Be
BeH
2
1s 2sp 2p
H H
p
x
p
x
+ =
+ = - =

1
=1 2
2s
+1 2
2 p
x

2
=1 2
2s
1 2
2 p
x
2sp
2
-orbitals
e.g. BH
3
B
1s 2s 2p
1s 2s 2p
1s 2sp
2
2p
B
B
H H
p
x
p
x
1s 2sp
2
2p
BH
3
H
BH
3
+ + =
+ +
+ +
=
=

1
=1 3
2s
+1 6
2 p
x
+1 2
2 p
y

2
=1 3
2s
+ 2(1 3
2 p
x
)

3
=1 3
2s
+1 6
2 p
x
+(1 2
2 p
y
)
2sp
3
-orbitals
e.g. CH
4
C
1s 2s 2p
1s 2s 2p
1s 2sp
3
2p
C
C
H H
p
x
p
x
1s 2sp
3
CH
4
H H
CH
4
+ +
+ +
-
-
- -
x
y
+
-
+z
-z

1
=1 4
2s
+1 4
2 p
x
+1 4
2 p
y
+1 4
2 p
z

2
=1 4
2s
+1 4
2 p
x
1 4
2 p
y
1 4
2 p
z

3
=1 4
2s
1 4
2 p
x
1 4
2 p
y
+1 4
2 p
z

4
=1 4
2s
1 4
2 p
x
+1 4
2 p
y
1 4
2 p
z
CH
3
CH
3
CH
2
=CH
2
CHCH
sp
3
-sp
3
sp
2
-sp
2
sp-sp
1s 2sp
3
CH
3
1s 2sp
2
CH
2
1s 2sp
CH
2p
2p
4
3 and
2 and 2
Multiple bonding in polyatomic molecules
HCN
C [He]2s
2
2p
2
N [He]2s
2
2p
3
H 1s
2
H
1s 2s 2p
H N C
2

H
N [He]2s
2
2p
3
1s 2s 2p
sp
3
lone pair
1s
O [He]2s
2
2p
2
1s 2s 2p
1s sp
2
two lone pairs
Examples: lone pairs in ammonia and water
Examples: Benzene, Conjugated polymers and resonance
p
x
p
x
p
x
p
x
p
x
p
x
p
x
p
x

p
x
p
x
p
x
p
x
p
x
p
x
p
x
p
x

p
x
p
x
p
x
p
x
p
x
p
x
p
x
p
x

C...C...C...C...C...C...C...C
C=C-C=C-C=C-C=C
C-C=C-C=C-C=C-C

Hybridization vs. Shape
sp s, p
x
2 linear
sp
2
s, p
x,y
3 trigonal-planar
sp
3
s, p
x,y,z
4 tetrahedral
sd
3
s, d
xy, xz, yz
4 tetrahedral
sp
2
d s, p
x,y,
d
xy, xz, yz
4 square-planar
sp
3
d s, p
x,y,z,
d
xy, xz, yz
5 square-pyramidal
sp
3
d s, p
x,y, z,
d
x2-y2
5 trigonal-bipyramidal
sp
3
d
2
s, p
x,y, z,
d
z2
6 octahedral
sp
3
d
3
7 pentagonal-bipyramidal
sp
3
d
4
8 square-antiprismatic
CO
2
CO
3
2-
BF
4
-
CrO
4
2-
[Pt
II
Cl
4
]
2-
Ni(PR
3
)
2
Br
3
PF
5
SF
5
IF
7
TaF
8
3-
Hybrid
Orbital used n Orientation Example
Group theory and Hybridization
Determine the shape of the molecule by VSEPR techniques and consider each sigma bond to the
central atom and each lone pair on the central atom to be a vector pointing out from the center.
Find the reducible representation for the vectors, using the appropriate group and character table,
and find the irreducible representations that combine to form the reducible representation.
The atomic orbitals that fit the irreducible representations are those used in the hybrid orbitals.
e.g. BH
3
1. VSEPR
x

BH
B
H
H
H
y
How many H-B bonds have been changed after applying the operation?
3 0 1 3 0 1
Summation of =s s=12
Now we reduce the reducible presentation to irreducible ones:

BH
3 0 1 3 0 1
1 2 3 1 2 3
1 1 1 1 1 1

BH
3 0 1 3 0 1
1 2 3 1 2 3
1 1 -1 1 1 -1

3 0 3 3 0 3
3 0 -3 3 0 -3
()/s = 12/s=12/12=1
0 A
2
`
1 A
1
`
()/s = 0/s=0/12=0
Finally after testing all the irreducible representation we obtain= A
1
`+E`
Related orbitals s from A
1
` p
x
p
y
or d
xy
d
x2-y2
from E` Hybridization sp
2
or sd
2
According to VSEPR of trigonal planar p is less energetic than d so the hybridization is sp
2
Molecular orbital (MO) theory : Homonucelar diatomic molecules: (chapter 2)
Molecular orbital (MO) theory : Heteronuclear diatomic molecules (chapter 2)
Molecular orbital (MO) theory: the ligand group orbital approach and application to triatomic molecules
Molecular orbital (MO) theory applied to the polyatomic molecules BH
3
, NH
3
and CH
4
Chapter 5 - Part 2
In molecular orbital (MO) theory, we begin by placing the nuclei of a given molecule
in their equilibrium positionsand then calculate the molecular orbitals (i.e. regions of
space spread over the entire molecule) that a single electron might occupy. Each MO
arises from interactions between orbitals of atomic centers in the molecule, and such
interactions are:
. Allowed if the symmetries of the atomic orbitals are compatible with one another;
. Efficient if the region of overlap between the two atomic orbitals is significant;
. Efficient if the atomic orbitals are relatively close in energy.
An important ground-rule of MO theory is that the number of MOs that can be formed
must equal the number of atomic orbitals of the constituent atoms.
You have to apply aufbau principles on MO as we did for atomic ones
MOLECULAR ORBITAL THEORY
Hydrogen
o
1s
*
o
1s
o
1s
*
o
1s
Antibonding (LUMO)
bonding (HOMO)
Bond order = (bonding-antibonding)
The symbol (*) instead of antibonding
Bond order= (2-0)=1 Bond order= (1-0)=
H
2
H
2
+
Bond energy=270 kJ/mol Bond energy=452 kJ/mol
2H
+
H
2
+
H
2 -452
-270
0 kJ
1s 1s 1s 1s
H : 1s
1
Bond length=74 pm Bond length=105 pm
o
1s
*
o
1s
o
1s
*
o
1s
Antibonding
bonding
Bond order= (2-2)=0 Bond order= (2-1)=
He
2
He
2
+
Bond energy=0.05 kJ/mol Bond energy=301 kJ/mol
1s
1s
1s 1s
Helium
Molecule not observed
THE MORE BOND ENERGY, THE MORE BOND STABILITY
p
x
p
y
p
z
Other Homonuclear Molecules
1s 1s
t
2 p
*
o
2s
*
o
2s
o
2 p
o
2 p
*
t
2 p
p
x
p
y
p
z
1s
o
2s
*
o
2s
p
x
p
y
p
z
B
2
, C
2
, N
2
O
2
, F
2
+

Linear Combination of Atomic Orbitals LCAO AO AO

p
+

+
+
+
+

+
+

2p
x
2p
y
2p
y
2p
x
1s
1s

s
*

s
2
p
*

p
*
2
p
Orbital
Potential
Energy
+ -
The s...s and p...p Overlaps
p
x
p
y
p
z
1s 1s
t
2 p
*
o
2s
*
o
2s
o
2 p
o
2 p
*
t
2 p
p
x
p
y
p
z
O
2
PARAMAGNETIC:
Unpaired electrons
Diradical
Magnetism in Oxygen
http://sol.sci.uop.edu/%7Ejfalward/magneticf
orcesfields/magneticforcesfields.html
The variation in orbital energies for Period 2 homonuclear diatomic molecules as far as F
2
O
2
F
2
Li
2
Be
2
B
2
C
2
N
2
1t
u
1t
g
2o
u
2o
g
1o
u
1o
g
o
g
, t
u
crossing
Bond order 1
2 2 0 1
1 3
Bond distance (pm)
Bond energy (kJ/mol)
267
121 124 - 141
159 110
110 498 607 - 159 297 945 MO s of Heteronuclear
MoleculesMOs of Heteronuclear
Molecules
The 2s orbital of the F atom has an energy about 27eV lower than that of the hydrogen
1s, so there is very little interaction between them. The F orbital retains a pair of
electrons. The F 2p
z
, orbital and the H 1s, on the other hand, have similar energies and
matching A, symmetries, allowing them to combine into bonding and antibonding
* orbitals. The F 2p
x
and 2p
y
orbitals have B
1
and B
2
symmetries and remain
nonbonding, each with a pair of electrons. Overall, there is one bonding pair of
electrons and three lone pairs.

*
1s
2p
2s
a
1
b
1
b
2
a
1
-13.6eV
-14.05eV
-40.17eV
H HF F
H F
H
H

HF
Molecular Orbitals and Photoelectron Spectrum of CO. Molecular orbitals l and
l* are from the 1s orbitals and are not shown, The el and e2 labels in the left-
hand column are for the C

symmetry labels; the bl and b2 labels are for C
2v
symmetry. (Photoelectron spectrum reproduced with permission from J. L.
Gardner and J. A. R. Samson, J. Chem. Phys., 1975,62,1447).
Bond order=(bonding-antibondig)=(8-2)=3
CO
- +
CO
CO
2
MOs of Polyatomic Molecules
2nodes
3nodes
1node
4nodes
2nodes
5nodes
3nodes
7nodes
3nodes
7nodes
3nodes
nonbonding
nonbonding
bonding
bonding
bonding
bonding
bonding
bonding
antibonding
antibonding
antibonding
antibonding
antibonding
antibonding
0 nodes
CO
2
O--O
O=C=O
CO
2
CO
2
- Bonding in CO
2
CO
2
Molecular orbitals of nonlinear molecules can be determined by the same procedures. Water will
be used as an example, and the steps of the previous section will be used.
1. Water is a simple triatomic bent molecule with a C2 axis through the oxygen and two mirror
planes that intersect in this axis. The point group is therefore C
2v
.
2. The C2 axis is chosen as the z axis and the xz plane as the plane of the molecule. Because the
hydrogen 1s orbitals have no directionality, it is not necessary to assign axes to the hydrogens.
3. Because the hydrogen atoms determine the
symmetry of the molecule, we will use their orbitals
as a starting point. The characters for each operation
for the Is orbitals of the hydrogen atoms can be
obtained easily. The sum of the contributions to the
character (I, 0, or - 1) for each symmetry operation
is the character for that operation, and the complete
list for all operations of the group is the reducible
representation for the atomic orbitals. The identity
operation leaves both hydrogen orbitals unchanged,
with a character of 2. Twofold rotation interchanges
the orbitals, so each contributes 0, for a total
character of 0. Reflection in the plane of the
molecule (
v
) leaves both hydrogens unchanged, for
a character of 2; reflection perpendicular to the
plane of the molecule (
v
') switches the two
orbitals, for a character of 0.
H
2
O
4. The representation can be reduced to the irreducible representations A
1
+B
1
, representing the symmetries of the
group orbitals. These group orbitals can now be matched with orbitals of matching symmetries on oxygen. Both 2s
and 2p
z
orbitals have A
1
symmetry, and the 2p
x
orbital has B
1
symmetry. In finding molecular orbitals, the first step is
to combine the two hydrogen 1s orbitals. The sum of the two, 1/2[(H
a
)+(H
b
)], has symmetry A
1
and the
difference, 1/2[(H
a
)-(H
b
)], has symmetry B
1
. These group orbitals, or symmetry-adapted linear combinations,
are each treated as if they were atomic orbitals, so they contribute equally to the group orbitals. The normalizing
factor is 1/2. In general, the normalizing factor for a group orbitals is N=1/(c
i
2
), where c
i
=the coefficients on the
atomic orbitals. Each group orbital is treated as a single orbital in combining with the oxygen orbitals.
5. The same type of analysis can be applied character when a p orbital changes sign. Each orbital can be treated
independently.
The s orbital is unchanged by all the operations, so it has A
1
symmetry.
The p
x
orbital has the B
1
symmetry of the x axis
The p
y
orbital has the B
2
symmetry of the y axis
The p
z
orbital has the A
1
symmetry of the z axis
The x, y, and z variables and the more complex functions in the character table assists in assigning representations to
the atomic orbitals.
6. The atomic group orbital combines with the same symmetry are combined into molecular orbitals. They are
numbered
1
through
6
in order of their energy, with 1 the lowest and 6 the highest
H
2
O
Hydrogen orbitals
E C
2

v

v
+1 +1 +1 +1
+1 -1 +1 -1
A
1
B
1
H+H
H-H
H
2
O
Oxygen orbitals
E C
2

v

v
+1 -1 +1 -1
+1 +1 +1 +1
+1 -1 -1 +1
+1 +1 +1 +1
A
1
s
B
2
p
x
A
1
p
z
B
1
p
y
H
2
O
C
2v
E C
2
v

v

A
1
1 1 1 1
A
2
1 1 -1 -1
B
1
1 -1 1 -1
B
2
1 -1 -1 1
Unchanged bonds
E C
2
v

v

O-H
2 0 2 0

O-H
=A
1
+B
1
means bonds (O of symmetry a
1
) and (H of symmetry a
1
)
H
2
O
H
2
O
D
3h
E 2C
3
3C
2
h
2S
3
3
v
A
1
` 1 1 1 1 1 1
A
2
` 1 1 -1 1 1 -1
E ` 2 -1 0 2 -1 0
A
1
`` 1 1 1 -1 -1 -1
A
2
`` 1 1 -1 -1 -1 1
E `` 2 -1 0 -2 1 0

B-H
=A
1
`+E`
Unchanged bonds
E 2C
3
3C
2
h
2S
3
3
v

N-H
3 0 1 3 0 1
x
y
BH
3
E C
3
C
3
2
C
2
(1) C
2
(2) C
2
(3)

h
S
3
S
3
2

v
(1)

v
(2)

v
(3)

1

1

2

3

1

3

2

1

2

3

1

3

2

2

3
LGO(1)=
1
+
2
+
3
+
1
+
3
+
2
+
1
+
2
+
3
+
1
+
3
+
2
=4
1
+4
2
+4
3
=1/3(
1
+
2
+
3
)
LGO(2)=1/6(2
1
-
2
-
3
)
LGO(3)=1/2(
2
-
3
)
2s orbital has a
1
` symmetry
E 2C
3
3C
2
h
2S
3
3
v
1 1 1 1 1 1
2p
z
orbital has a
2
` symmetry
1 1 -1 1 1 -1
2 -1 0 2 -1 0 2p
x
and 2p
y
orbital has e` symmetry
B
BH
3
LGO(1) orbital has a
1
` symmetry
E 2C
3
3C
2
h
2S
3
3
v
1 1 1 1 1 1
2 -1 0 2 -1 0
LGO(2) and LGO(3) orbital has e`
symmetry
nonbonding
doesnt belong to a
1
`+e`
C
3v
E 2C
3
3C
2
A
1
1 1 1
A
2
1 1 -1
E 2 -1 0

N-H
=A
1
+E
Unchanged bonds
E 2C
3
3C
2

N-H
3 0 1
NH
3
NH
3
2p
z
and 2s orbital has a
1
symmetry
2 -1 0 2p
x
and 2p
y
orbital has e symmetry
LGO(1) orbital has a
1
symmetry
LGO(2) and LGO(3) orbital has e symmetry
doesnt belong to a
1
+e
x
y
E 2C
3
3C
2
1 1 1
1 1 1
C
3v
E 2C
3
3C
2
1 1 1
1 1 1
NH
3
Packing of spheres
The packing-of-spheres model applied to the structures of elements
Polymorphism in metals
Metallic radii
Melting points and standard enthalpies of atomization of metals
Alloys and intermetallic compounds
Bonding in metals and semiconductors
Semiconductors
Sizes of ions
Ionic lattices
Crystal structures of semiconductors
Lattice energy: The Born-Haber cycle
Lattice energy: calculated versus experimental values
Applications of lattice energy
Defects in solid state lattices
Structures and energetics of metallic and ionic solids Chapter 6
Structures of the 14 possible crystal structures (Bravais lattices)
Bravais Lattices
x
y
x
z
A AB ABA
A AB ABC
x
z
x
y
Packing of Spheres
Hexagonal close packing (hcp)
Cubic close (ccp) or
face-centered (fcc) packing
Cube
Octahedral hole
Tetrahedral
hole
Simple Cubic non-close Packing Body-Centered Cubic non-close Packing
The Packing-of-Spheres Model Applied to the Structures of
Elements
Group 18 Elements ccp (except He)
H
2
and F
2
hcp,packing-of-spheres model to the crystalline structures of such
molecules is only valid because they contain freely rotating molecules
Metallic elements
h hexagonal closet-packing
cubic closet-packing
body-centered cubic packing
structures type of its own
* slightly distorted
If a substance exists in more than one crystalline form, it is polymorphic.
*
*
*
*
*
r
a
r
a
c
b
r
a
b
scc
a=2r
bcc
b
2
=a
2
+a
2
c
2
=a
2
+b
2
= 3a
2
c= 3a=4r
a=
4r
3
fcc
b
2
=a
2
+a
2
16r
2
=2a
2
a= 8r
Relationship between Atomic Radius and the Edge Length in Three Different Unit Cells
Gold (Au) crystallizes in a cubic close-packed structure (the face-centered cubic unit cell) and has a density of
19.3 g/cm3. Calculate the atomic radius of gold in picometers and its percentage occupancy.
density of density of
unit cell unit cell
Volume of Volume of
unit cell unit cell
Edge of unit Edge of unit
cell cell
Radius of Radius of
Au atom Au atom

Edge

Face
Corner
Body (Center)
Corner=18 atom
Edge=14 atom
Face=12 atom
Center=1 atom
Atoms per unit cell
Atoms per unit cells=how many atoms can be situated inside a
unit cell (fractions are permitted)
8*(1/8)+6*(1/2)=4 atoms per unit cell
Mass of the unit cell=
4 atoms
1 unit cell

1 mol
6.022 10
23
atoms

197.0g Au
1 mol Au
=1.3110
31
g/unit cell
Volume of the unit cell=
m
d
=
1.3110
31
19.3 g/cm
3
= 6.79 10
23
cm
3
a = V
3
= 6.79 10
23
cm
3 3
= 4.08 10
8
cm
r =
a
8
=
4.08 10
8
cm
8
=1.44 10
8
cm=144pm
8r = a
( 8)
3
r
3
= a
3
~ 22.63r
3
(Atoms per unit cell) *
4
3
tr
3
=
16
3
tr
3
~ 16.76r
3
Unit cell edge length=
Unit cell volume=
The unit cell contains 4 spheres, and the volume of a sphere=4/3r
3
Volume of the unit cell occupied=
Percentage occupancy=Volume of the unit cell occupied/Unit cell volume*100%=16.76/22.63*100%=74%
Atomic Radii and Percentage occupancy
Holes occupancy=1-74%=26%
Pauling considered a series of alkali metal halides, each member of which contained isoelectronic
ions (NaF, KCl, RbBr, CsI). In order to partition the ionic radii, he assumed that the radius of
each ion was inversely proportional to its actual nuclear charge less an amount due to screening
effects (can be calculated using Slater's rules).
For example, the difference in anion-cation distance between the halides NaX and KX is close to
36 pm irrespective of the anion X, and it is natural to attribute this to the difference in radii
between Na
+
and K
+
. To separate the observed distances into the sum of two ionic radii is,
however, difficult to do in an entirely satisfactory way. One procedure is to look for the
minimum value in the electron density distribution between neighboring ions, but apart from the
experimental difficulties involved such measurements do not really support the assumption of
constant radius. Sets of ionic radii are therefore all based ultimately on somewhat arbitrary
assumptions. Several different sets have been derived, the most widely used being those of
Shannon and Prewitt, based on the assumed radius of 140 pm for O
2
in six-coordination.
Goldschmidt and, more recently, Shannon and Prewitt, concentrated on the analysis of
experimental data (mostly fluorides and oxides) with the aim of obtaining a set of onic radii
which, when combined in pairs, reproduced the observed internuclear distances, they found that
rion for a given ion increases slightly with an increase in coordination number.
Cation Li
+
Na
+
K
+
Rb
+
Cs
+
r+/pm 76 102 138 149 170
Anion F
-
Cl
-
Br
-
I
-
r-/pm 133 181 196 220
Ionic Radii
2r
x-
d=2r
x-
+2r
x+
d
Li
+
Cl
-
Ionic Radii Ratio
For LiF, this corresponds to an NaCl type lattice, in
agreement with the observed structure. In fact each of
the group 1 halides (except CsCl, CsBr and CsI) at
298K and 1 bar pressure adopts the NaCl type
structure; CsCl, CsBr and CsI adopt the CsCl type
lattice. Radius ratio rules predict the correct structures
in only some cases; they predict tetrahedral
coordination for the cations in LiBr and LiI, and cubic
coordination in NaF, KF, KCl, RbF, RbCl, RbBr and
CsF (in addition to CsCl, CsBr and CsI).
Metallic Radii
CN=how many atoms can make bond with the cation/anion
* Inorganic Chemistry, Houescroft and Sharpe page 153
2r
metal
Coordination number
Relative Radius
12 8 6 4
1.00 0.97 0.96 0.88
For example in the case of K (potassium) the lattice system is
cubic body centered=K with 8 other K around.
r
12coordiante
r
8coordinate
=
1
0.97
From Table 6.2 * r
8coordinate
= 0.97 *r
12coordinate
= 0.97 *235 = 228pm
Binary compounds (compounds consisting of two elements) may have very simple crystal structures and
can be described in several different ways. If the larger ions (usually the anions) are in close-packed
structures, ions of the opposite charge occupy these holes, depending primarily on two factors:
1. The relative sizes of the atoms or ions. The radius ratio (usually r+/r- but sometimes r-/r+, where r+
is the radius of the cation and r- is the radius of the anion) is generally used to measure this. Small
cations will fit in the tetrahedral or octahedral holes of a close-packed anion lattice. Somewhat larger
cations will fit in the octahedral holes, but not in tetrahedral holes, of the same lattice. Still larger cations
force a change in structure.
2. The relative numbers of cations and anions. For example, a formula of M
2
X will not allow a close-
packed anion lattice and occupancy of all of the octahedral holes by the cations because there are too
many cations. The structure must either have the cations in tetrahedral holes, have many vacancies in the
anion lattice, or have an anion lattice that is not close-packed
Binary compounds
NaCl is made up of face-centered cubes (fcc) of sodium ions and face-centered cubes of chloride ions combined, but offset by
half a unit cell length in one direction so that the sodium ions are centered in the edges of the chloride lattice (and vice versa). If
all the ions were identical, the NaCl unit cell would be made up of eight simple cubic unit cells. Many alkali halides and other
simple compounds share this same structure. For these crystals, the ions tend to have quite different sizes, usually with the anions
larger than the cations. Each sodium ion is surrounded by six nearest-neighbor chloride ions, and each chloride ion is surrounded
by six nearest-neighbor sodium ions.
Na
+
Cl
-
Corner
Edge
Face
Center
Total
Na
+
Cl
-
8 0
0
6
0
12
0
1
8*1/8=1 Na
+
12*1/4=3 Cl
-
6*1/2=3 Na
+
1*1=1 Cl
-
4 Na
+
and 4 Cl
-
CN 6 6
Cation is small
Anion is large
Corner
Edge
Face
Center
Total
Cs
+
Cl
-
8 0
0
0
0
0
0
1
8*1/8=1 Cs
+
0*1/4=3 Cl
-
0*1/2=3 Cs
+
1*1=1 Cl
-
1 Cs
+
and 1 Cl
-
CN 8 8
As mentioned previously, a sphere of radius 0.73r will fit exactly in the center of a cubic
structure. Although the fit is not perfect, this is what happens in CsCl where the chloride
ions form simple cubes with cesium ions in the centers. In the same way, the cesium ions
form simple cubes with chloride ions in the centers. The average chloride ion radius is 0.83
times as large as the cesium ion (167 pm and 202 pm, respectively), but the inter-ionic
distance in CsCl is 356 pm, about 3.5% smaller than the sum of the average ionic radii.
Only CsCl, CsBr, Csl, TlCl, TlBr, TII, and CsSH have this structure at ordinary
temperatures and pressures, although some other alkali halides have this structure at high
pressure and high temperature. The cesium salts can also be made to crystallize in the NaCl
lattice on NaCl or KBr substrates, and CsCl converts to the NaCl lattice at about 469C.
Cation is large
Anion is large
The wurtzite form of ZnS is much rarer than zinc blende, and is formed at higher temperatures
than zinc blende. It also has zinc and sulfide each in a tetrahedral hole of the other lattice, but each
type of ion forms a hexagonal close-packed lattice. As in zinc blende, half of the tetrahedral holes
in each lattice are occupied.
S
Zn
One sulfide layer and one zinc layer of wurtzite. The
third layer contains sulfide ions, directly above the
zinc ions. The fourth layer is zinc ions, directly above
the sulfides of the first layer.
ZnS has two common crystalline forms, both with coordination number
4. Zinc blende is the most common zinc ore and has essentially the
same geometry as diamond, with alternating layers of Zn and S. It can
also be described as having zinc ions and sulfide ions, each in face-
centered lattices, so that each ion is in a tetrahedral hole of the other
lattice. The stoichiometry requires half of these tetrahedral holes to be
occupied, with alternating occupied and vacant sites.
diamond ZnS blend
ZnS wurtzite
The fluorite structure can be described as having the calcium ions in a cubic close-packed lattice, with
eight fluoride ions surrounding each one and occupying all of the tetrahedral holes. An alternative
description of the same structure has the fluoride ions in a simple cubic array, with calcium ions in
alternate body centers. The ionic radii are nearly perfect fits for this geometry. There is also an
antifluorite structure in which the cation-anion stoichiometry is reversed. This structure is found in all
the oxides and sulfides of Li, Na, K, and Rb, and in Li
2
Te and Be
2
C. In the antifluorite structure,
every tetrahedral hole in the anion lattice is occupied by a cation, in contrast to the ZnS structures, in
which half the tetrahedral holes of the sulfide ion lattice are occupied by zinc ions.
Fluorite shown as Ca
2+
in a cubic close packed lattice,
each surrounded by eight F
-
in the tetrahedral holes.
Ni
As
TiO
2
in the rutile structure has distorted TiO
6
octahedra that form columns by sharing edges, resulting
in coordination numbers of 6 and 3 for titanium and oxygen, respectively. Adjacent columns are
connected by sharing corners of the octahedra. The oxide ions have three nearest-neighbor titanium
ions in a planar configuration, one at a slightly greater distance than the other two. The unit cell has
titanium ions at the corners and in the body center, two oxygens in opposite quadrants of the bottom
face, two oxygens directly above the first two in the top face, and two oxygens in the plane with the
body-centered titanium forming the final two positions of the oxide octahedron. The same geometry is
found for MgF
2
, ZnF
2
, and some transition metal fluorides. Compounds that contain larger metal ions
adopt the fluorite structure with coordination numbers of 8 and 4.
The nickel arsenide structure has arsenic atoms in identical close-packed layers stacked directly over
each other, with nickel atoms in all the octahedral holes. The larger arsenic atoms are in the center of
trigonal prisms of nickel atoms. Both types of atoms have coordination number 6, with layers of
nickel atoms close enough that each nickel can also be considered as bonded to two others. An
alternate description is that the nickel atoms occupy all the octahedral holes of a hexagonal close-
packed arsenic lattice. This structure is also adopted by many MX compounds, where M is a
transition metal and X is from Groups 14, 15, or 16 (Sn, As, Sb, Bi, S, Se, or Te). This structure is
easily changed to allow for larger amounts of the nonmetal to be incorporated into nonstoichiometric
materials.
Ti
O
NiAs - a semiconductor
Rutile
Perovskite is an example of a double oxide; it does not, as the formula might imply, contain[TiO
3
]
2-
ions, but is a mixed Ca(II) and
Ti(IV) oxide.
Many double oxides or fluorides such as BaTiO
3
, SrFeO
3
, NaNbO
3
, KMgF
3
and KZnF
3
crystallize with a perovskite lattice.
Deformations of the lattice may be caused as a consequence of the relative sizes of the ions, e.g. in BaTiO
3
, the Ba
2+
ion is relatively
large (rBa
2+
=142pm compared with rCa
2+
=100 pm) and causes a displacement of each Ti(IV) centre such that there is one short TiO
contact. This leads to BaTiO
3
possessing ferroelectric properties
The structures of some high-temperature superconductors are also related to that of perovskite. Another mixed oxide lattice is that of
spinel, (complicated structure and its structure will not be drawn here) MgAl
2
O
4
.
Corner
Edge
Face
Center
Ba
2+
O
2-
0 0
0
0
1
0
6
0
1*1=1 Ba
2+
6*1/2=3 O
2-
8*1/8=1 Ti
+
CN 6 2
Perovskite
Ti
+
8
0
0
0
8
ccp (fcc)
BaTiO
3
a ferroelectric complex
CdI
2
Graphite
SiO
3
2-
Si
2
O
5
2-
SiO
3
2-
Si
4
O
11
6-
Si
6
O
18
12-
Si
3
O
9
6-
Common Silicate Structures
Quartz
=
Consider the first tetrahedron in the chains of SiO
3
2-
to have four oxygen atoms, or SiO4. Extending the
chain by adding SiO
3
units with the fourth position sharing an oxygen atom of the previous tetrahedron
results in an infinite chain with the formula SiO
3
. The charge can be calculated based on Si
4+
and O
2-
.
Si
2
O
5
2-
can be described similarly. Beginning with one Si
2
O
7
unit can start the chain. Adding Si
2
O
5
units
(two tetrahedra sharing one corner and each with a vacant comer for sharing with the previous unit) can
continue the chain indefinitely. Again, the charge can be calculated from the formula.
-cristoballite
Alloys and Intermetallic Compounds
Substitutional alloys:
In a substitutional alloy, atoms of the solute occupy sites in the lattice of solvent metal, e.g. Sterling Silver (92.5% Ag and 7.5% Cu)
1. Both metals must have the same lattice (ccp, hcp...etc)
2. radius of the first metal is approximately equal to the other.
Interstitial alloys:
In a interstitial alloy, atoms with small radius occupy the
octahedral holes, e.g. Stainless steel Cr in Fe and Carbon
steel (see Box 6.2 page 159, of Inorganic chemistry
Housecroft and Sharpe)
Intermetallic compounds:
When melts of some metal mixtures solidify, the alloy formed may possess a definite structure type that is different from those of the
pure metals. e.g. CuZn (-Brass)
Replace (an) atom(s) from
the lattice by different one
Insert (an) atom(s) in the
lattice.
Metals
Explain why metals are usually lustrous (mirror-like)
In the band model there is a continuum of empty energy levels rather than discrete energy levels. Thus light quanta of all energies
within a wide range of wavelengths will be absorbed equally, and then the energized electrons will re-emit the light when they
fall back into their ground-state orbitals. This is the mechanism for reflection of light of all frequencies, which we call "luster".
Predict how the Group II metals differ from group I in density, melting point, and mechanical strength.
In any given period the Group II ions are smaller and may thus approach each other more closely. At the same time twice as
many electrons are present sea. The closer approach and the much greater electrostatic interactions between the 2+ ions and the
sea of high negative charge density lead to greater density and much greater bonding energy, which in turn leads to much higher
melting point and hardness. Actually going from Group I to Group II increases the density by a factor of about 2 and raises the
melting point by hundreds of degrees.
Metals usually feel cool to the touch compared with other materials because they are such good conductors of heat. How
can we explain this unusual thermal conductivity?
In most materials heat is conducted by atom-to-atom transfer of vibrational motion from the hot end to the cold end. In metals the
thermal energy is transferred primarily by the motion of the electron sea's free electrons, which are very mobile.
Conductors
Li Li Li Li
Li Li Li Li Li Li
Li Li Li Li Li Li Li Li
Li Li Li Li ..... .....
6.022 6.022 10 10
23 23
Li (metallic solid) Li (metallic solid)
Li
2
Li
3
Li
4
Li
Avogadro
empty orbitals empty orbitals
filled orbitals filled orbitals
In any solid, metallic, ionic or covalent the valence
orbitals of atoms and molecules combine to form
molecular orbitals. The number of molecular orbitals
is equal to the number of atomic orbitals, and for any
material, this is a very large number but the energy
difference between highest and lowest doesn't change
by much. Many orbitals separated by very small
energy gaps give rise to bands of orbitals.
For lithium metal, the band is made up of molecular
orbitals formed from the combination of 2s atomic
orbitals and about half of the orbitals are filled. There
is only a very small energy gap between the highest
occupied molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO). When an
electron goes to an unoccupied orbital with available
thermal energy, it is free to travel throughout the
metal. The "hole" left in the HOMO can travel too.
Band gap
Bandgap
Fermi Level
E
l
e
c
t
r
o
n
i
c

(
o
r
b
i
t
a
l

e
n
e
r
g
y
)
nonmetallic band picture metallic solid band picture
electron sea are in blue color
The band gap in a nonmetallic solid is important for electrical
and optical properties. A solid with a small band gap is a
semiconductor with a conductivity that (unlike the case with a
metal) increases as temperature is raised. The band gap also
determines the minimum photon energy required to excite an
electron from the valence band (VB) to the conduction band
(CB), and hence the threshold for optical absorption by a solid.
VB
CB
In silica (SiO
2
) there are covalent bonds between each silicon and 4 oxygens around it that are
combinations of Si 3s and 3p atomic orbitals and O 2s and 2p atomic orbitals. We can think of the
molecular orbitals forming similar bands but there is a large energy separation or band gap between the
occupied and unoccupied levels. The electrons in the orbitals of silica are not free to travel and the
material is an insulator.
In pure, crystalline silicon, there is also a band gap between the occupied and unoccupied molecular
orbitals but it is smaller. Electrons in the filled valence band can be promoted to the conduction
band by thermal energy or when the material absorbs light. The electrons would then be free to travel
through the material and holes (electron vacancies) would travel through the valence band.
Semiconductors
Intrinsic semiconductors: pure semiconductors e.g. C, Si, Ge and a-Sn
Extrinsic (n- and p-type) semiconductors: extrinsic semiconductors contain dopants; a dopant is an impurity
introduced into a semiconductor in minute amounts to enhance its electrical conductivity, e.g. Ge-doped Si.
Doping involves the introduction of only a minutely small proportion of dopant atoms, less than 1 in 10
6
, and
extremely pure Si or Ge must first be produced.
Acceptor level
Small band gap
}
p-type
Small band gap
Donor level
}
n-type
In a p-type semiconductor (e.g. Ga-doped Si),
electrical conductivity arises from thermal
population of an acceptor level which leaves
vacancies (positive holes) in the lower band.
In an n-type semiconductor (e.g.
As-doped Si), a donor level is
close in energy to the conduction
band.
Carbon in diamond form is an
insulator with extremely high
resistivity. But in graphite form its
interatomic spacing is larger, making
the band gap small enough to support
some electrical conduction
Used as p-dopants
to produce p-type
semiconductors
Tin can be considered to be a
semiconductor with a very small
band gap, but at room temperature
it supports metallic conduction
Silicon and germanium are
the intrinsic semiconductors
employed in solid state
electronics.
Used as n-dopants
to produce n-type
semiconductors.
The bands overlap in
lead, making it metallic
conductor.
B
C
2p
2
N
Al
Si
3p
2
P
Ga
Ge
4p
2
As
In
Sn
5p
2
Sb
Tl
Pb
6p
2
Bi
The electrical conductivity of a metal decreases
with temperature
A metal is characterized by the fact that its
electrical resistivity increases as the temperature
increases, i.e. its electrical conductivity decreases
as the temperature increases.
The electrical conductivity of a semiconductor
increases with temperature.
Resistivity: Conductors vs. Semiconductors
The degree to which a substance or device opposes the passage of an
electric current, causing energy dissipation. Ohm's law resistance
(measured in ohms) is equal to the voltage divided by the current.
ohms
Perovskites MgB
2
Cu
Y
Ba
Mg
B
YBa
2
Cu
3
O
7
The conductivity of metals and of semiconductors changes with temperature. Why? It's because the
electrons flowing through a material will always pass close by positively charged nuclei. This impedes
flow. As temperature increases, there is more thermal motion of the nuclei and this resistance increases.
Resistivity is a property of the metal or semiconductor. In superconductors, the resistivity goes to zero at
some temperature.
Some of the recently discovered high temperature superconductors are based on perovskites. You drew the
lattice of CaTiO
3
last week and most of you drew a cubic lattice of Ca with Ti in the cubic hole and oxygen
atoms on the edges. Another perovskite with the same structure is BaCuO
3
You could also draw the same
lattice as a cubic array of copper atoms. Now imagine that some of the oxygen atoms have been removed
and 1/3 of the barium atoms have been exchanged for yttrium. You would have the basic structure of a 1-2-
3 material or YBa
2
Cu
3
O
7
.
Superconductors
Lattice Energy
The energy of the crystal lattice of an ionic compound is the energy released
when ions come together from infinite separation to form a crystal:
M
(g)
+
+X
(g)
-
MX
(s)
In the crystal lattice there are more interactions. The summation of all of these geometrical
interactions is known as the Madelung constant, A. The energy then can be expressed as following:
From Coulombs law, the attraction is obtained as following:
E
c
=
Z
+
Z

4tc
0
r
The energy increases as the interionic distance decreases.
It is common to express Z+ and Z- as multiples of electronic charge:
E
c
=
e
2
Z
+
Z

4tc
0
r
E
c
=
Ae
2
Z
+
Z

4tc
0
r
Madelung Constant
a distance r
a distance 2 r
a distance 3 r
a distance 4 r=2r
6X
z
12M
z+
8X
z
6M
z+
AU =
e
2
4tc
0
[(
6
r
z
+
z

) (
12
2r
z
+
z
+
)+(
8
3r
z
+
z

) (
6
4r
z
+
z
+
)...]
AU =
e
2
4tc
0
[(
6
r
z
+
z

) (
12
2r
z
+
2
)+(
8
3r
z
+
z

) (
6
4r
z
+
2
)...]
AU =
z
+
z

e
2
4tc
0
r
[6 (
12 z
+
2 z

)+(
8
3
) (3
z
+
z

)...]
.
.
.
.
.
.
Madelung Constant
AU =
z
+
z

e
2
4tc
0
r
[6 (
12 z
+
2 z

)+(
8
3
) (3
z
+
z

)...]
z
+
z

=1 for NaCl
AU =
z
+
z

e
2
4tc
0
r
[6
12
2
+
8
3
3...]
AU =
N
Avogadro
A z
+
z

e
2
4tc
0
r
A Madelung constant.
N
Avogadro
Avogadros number=6.0223x10
23
atom/mol
|z
+
| e.g. NaCl; Na has a charge of +1 then |+1|=1
|z
-
| e.g. NaCl; Cl has a charge of -1 then |-1|=1
e 1.602x10
-18
C

0
permittivity of vacuum=8.854x10
-12
Fm
-1
r the ionic radius
Lattice type A
Sodium chloride (NaCl) 1.7476
Caesium chloride (CsCl) 1.7627
Wurtzite (-ZnS) 1.6413
Zinc blend (-ZnS) 1.6381
Fluorite (CaF
2
) 2.5194
Rutile (Ti
2
O) 2.408
Cadmium iodide (CdI
2
) 2.355