MAT1220/Electrical/Lecture 3 Molecular Orbital Theory: A few simple rules

• n AO produce n MO. Can’t create or destroy orbitals

• Need only consider the valence AO’s.
• Need to consider the relative energy of valence AO’s on the atoms.
• Need to consider the symmetry and overlap of AO’s. (For solids this
means the crystal structure and ionic radii of the ions are important.
For molecules this means molecular shape and bond lengths are
important).
• In polyatomic molecules, a greater variety of MO’s can be formed.
• As the molecules become larger, their MO’s become more
numerous, and more closely spaced in energy (see next Figure).
• MOT emphasises the delocalised nature of the electron distribution,
so that MO’s are generally extended over all the constituent atoms.
• The orbitals that extend throughout the molecule or solid can be
called crystal orbitals. They are the property of the molecule/solid and
not individual atoms/ions. They form bands over certain energy levels.
 Orbital energies.
(c) (d) (e)
(b)
CB Conduction Band
(a)
Eg Energy Gap

VB Valence Band
Energy
(a) AO energy of atom, X
(b) MO energies of a small molecule, Xn ( n =2)
(c) MO energies of a large molecule, Xn (n > 5)
(d) MO energies of solid X
(e) Density of states for (d). [N(E) – Within the allowed bands, more orbitals
are concentrated together at some energies compared to others. N(E) is
zero in the band gap between the VB and CB.
• Valence Band (VB): from occupied electron orbitals in the ground state.
• Conduction Band (CB): from empty orbitals in the ground state.
 • The width of a particular band is related to interatomic separation and
hence on the degree of overlap between orbitals on adjacent atoms.
• Strong overlap gives wide bands whereas small overlap gives narrow
bands.
s- and p-block metals are excellent examples of ‘wide band’ solids.
Na Metal. 1s22s22p63s13p0

core valence
• Metals may be regarded as infinitely large ‘molecules’ in which an enormous
number of energy levels or MO is present, ~ 6 x 1023 for one mole of metal.
• Valence s and p orbitals, especially in the metallic elements on the left-hand
side of the periodic table overlap strongly to give bands which are many eV in
width. Commonly 6-8 eV. Contracted core orbitals give very narrow bands
(less than 0.1 eV wide). These retain their atomic identity in solids and do not
contribute to the bonding.
• If these bands are partially filled by valence electrons then electron
delocalisation throughout the solid can occur and results in metallic
conductivity.
 Band picture for Na metal

Energy

↑
Ef

‘Isolated Na atom’ Na solid

Partially filled VB.
(discrete AO’s) (Wide energy band)
• Smearing out of AO energy levels when forming the solid produces a wide
energy band of available electron energies (a continuum of ~ 6-8 eV)
• This band (or crystal orbital) is a property of the solid.
• Each Na atom has 1 valence electron to contribute to the band.
• How many electrons/Na atom can the band hold? 8 e-
• The band is 1/8th full.
• Fermi Level, Ef : energy where the probability of electron occupation is 1/2,
i.e. half of the energy levels with this energy are empty.
 Na metal

Many s- and p-block elements are metals because

they produce partly filled, wide energy bands for
(a) valence electrons and therefore electron delocalisation
Ef through the solid. Examples, Li, Na, Ca, Sr, Al….

(b)
• (a) Only electrons close to Ef contribute to conductivity. Thermal energy
at 300 K is ~ 0.04 eV but this is sufficient to promote electrons into
‘empty’ energy levels above Ef and therefore delocalise throughout the
solid.
• (b) electrons near the bottom of the band have little contribution to the
conductivity of the solid.
• In a metal not carrying a current the average velocity of all the electrons
sums to zero.
• When an electric field (Eapp) is applied, each electron experiences a
force –qEapp and a change in velocity. The velocities no longer sum to
zero and electrons drift in a direction opposite to that of Eapp. A current
then flows.
 The influence of interatomic separation.

Diagram shows the effect of interatomic

spacing on AO energy levels and bands for
Na, calculated using the tight binding theory.
Shaded regions represents bands of energy
levels formed by significant overlap of AO on
adjacent atoms. (Fig. from West)

• Diagram shows the width of a particular energy band is related to the

interatomic separation and therefore the degree of overlap between orbitals
on adjacent atoms.
• ro – interatomic separation at STP. 3s and 3 p form broad bands that
overlap. 1s, 2s and 2p orbitals on adjacent atoms do not overlap Instead of
forming bands they remain as discrete AO’s on individual atoms. They are
represented as thin lines.
• r’ – compression of Na using pressure to reduce interatomic separation,
then 2s and 2p orbitals would overlap to form bands of energy levels.
• Some materials can become ‘metallic’ conductors under pressure.
 How close are we to the holy grail of room temperature superconductivity?
1911- Low Tc

1986- High Tc
Tc <23 K Tc > 23 K > 100 GPa!
2015 – High P
Low Tc High Tc High P-Tc
300 Room
Temp
H2S, P = 1.5 M x Sea level pressure!
200
Tc (K) CSHx = CH4 + H2S + H2 (Tc = 288K)

100
5 N2 (liq)
0
4 ($ 0.30/litre)
0
3
0
2
0 H2 (liq)
1
0
0 He (liq)
1900 1985 2015
Future: two elements with H2
2020 ($ 15/litre)
Year

https://www.forbes.com/sites/startswithabang/2021/07/07/how-close-are-we-to-the-holy-grail-of-room-temperature-
superconductors/?sh=4d9a22048665
 Conductivity and resistance of metals
• Resistance is caused by interactions of electron with atoms or
defects. These are known as phonons

So ρ = f (T, [impurity], [defect])

• All contributions are additive, the phenomenon being known as

Matthieson’s Rule

So ρtotal = ρTemp + ρimpurities + ρdefects

• Matthiessen's rule states that the total resistivity for a sample is the
sum of all of the individual contributions. A metal with a lower value
for resistivity, has a lower resistance to DC current flow. The bulk
resistivity for several common metals is shown below:

Metal Resistivity, ρ (mWcm)

Al 2.73 Cu 1.73 Ag 1.63 Au 2.27
 Temperature dependence of resistivity, ρTemp
• Conventional Metals
Current flow in conventional metals is a result of the movement of
electrons under the influence of an applied electrical field. The electrons
flow through the metal is impeded by the presence of resistance, which
results from the scattering of electrons. Thus, electron scattering results
in electrical resistance. Resistance can also be caused by defects in the
metal, such as impurities and grain boundaries. Scattering from such
defects results in extrinsic resistance.
Slope = a Resistivity of a metal
increases with temperature

ρ =ρ (1+ aΔT)
ρ T 25
Due to electron-phonon interactions,
i.e. e- bump into the lattice.
Atomic vibrations increase with
T temperature hence more interactions.
• The constant a is associated with the thermal vibrations of atoms and
also with thermally generated defects. For Cu, α = 0.0068 oC-1
• Values need to be determined experimentally
 ρimpurities
• In simple homogeneous alloy systems where the impurities are
present at low levels with concentration c
then ρimpurities =A c (1-c)
A is a constant depending on the host metal and on the impurity

• Note: ρimpurities is independent of temperature

• The term c(1-c) is characteristically

‘domed’ when ρ is plotted against c
ρ ρCu (300K) = 1.6 x 10-6 Ωcm but
ρCu0.5/Ni0.5 (300K) = 4.7 x 10-5 Ωcm
• So ρ increases approx 30 times when Ni
is alloyed with Cu in a homogeneous
0 C 100 solid solution.
Metal alloy
• In some cases, alloys are heterogeneous
solutions and then overall resistivity is the
sum of two fractional components.
ρ = ρaVa + ρbVb
 ρdeformation

• Any working of metal gives rise to defects or dislocations and

therefore ρdeformation increases.

• Its effect is smaller than ρtemp and ρimpurities

Electrical properties of commercial metals and alloys

• Most widely used metallic conductor is Cu.
Ag > Cu but the difference is not great and Cu is much less expensive
Al ~ 0.5 Cu but weight is a key factor
• But to obtain high conductivity, , the metal needs to be pure and O2 free.

Pure metals are soft and prone to deformation and therefore a decrease
in conductivity

Ways to improve this are: (i) solid solution alloy

(ii) dispersed second phase (little effect)
(iii) cold working (can give lower )