SPCS Department of Chemistry

SEF043 - SUMMARY

Molecular Orbital Theory

Gas Law
Intermolecular-Intramolecular Forces
 Concepts Learning Objectives

 Steps towards constructing the Molecular orbital  Construct molecular orbitals of simple Homonuclear
diagram diatomic molecules
 Homonuclear diatomic molecules with MOs
originating from s orbitals
 To identify if there is sp mixing
 Homonuclear diatomic molecules with MOs
originating from s and p orbitals  To work out questions with Gas Law
 To recognise the type of forces between molecules
 What is sp mixing?
 Mentimeter and exam-type questions
 Gas Law
 Intermolecular and Intramolecular Forces
 An overview
Lewis Structure
To put all the electrons together to allow for the Octet to happen.
But it does not provide any information on the Geometry of the molecule.

VSEPR
Based on the repulsion between electron pairs. It provides an easy qualitative prediction of structures.

But does not provide insight into the bonding.

Molecular Orbital
Based on the overlap between atomic orbitals of constituent atoms. It provides a good description of bonding.

But is difficult to use for the prediction of structures.

Hybridisation
Is based on the idea of a localised, 2-electron bond with bond description in terms of orbital overlap. It predicts the

structure.
 Why Molecular Orbital Theory?
1) Draw a framework structure. H and F are always
terminal. And atoms with lowest electronegativity goes in
the middle

2) Count the total number of valence electrons:

6+6=12

3) Count the total number of electrons 8+8=16

needed for the OCTET

4) Number of bonding electrons:Subtract the number oftotal
electrons for full shells from the number of valence 16-12=4
electrons
5) Assign 2 bonding electrons to each bond. OK

6) If bonding electrons remain, make some double or

Yes, 4-2=2 OK go for double bond
triple bonds.

7) Number of lone pairs: Valence electrons [step 2] 12-4=8

minus Bonding electrons [step 4].
8) Determine formal charges.
 Why Molecular Orbital Theory?

1) The Lewis model for covalent bonding was a brilliant but flawed model.
2) It could not account for the magnetism of O2.
3) Diamagnetic materials will repel a magnet, and all electrons are paired.
4) Yet O2 is magnetic, a property that implies the presence of unpaired
electrons.
5) We need another model to explain O2.
 Molecular Orbital Theory

Quantum mechanics helps us describe the behaviours of an electron in an atom by a

wave function, which is called an atomic orbital.
The Linear combination of the atomic orbitals (LCAO) gives rise to molecular orbitals.

 The likelihood (probability) of finding a valence electron in a region of space in a molecule is called
a molecular orbital
 A molecular orbital describes the distribution of electrons in molecules like the distribution of
electrons in atoms.
 N atomic orbitals N molecular orbitals.
 Combination of S orbitals

Constructive interference
Destructive interference
 Combination of P orbitals

Constructive interference
Destructive interference
 How to Construct Molecular Orbital?

1. We represent the total energy of the orbitals by an arrow

2. We locate the individual atomic orbitals (AO) on the left and right sides of
the diagram
3. We locate the molecular orbitals in the middle of the diagram
4. The bonding orbitals are more stable and lower in energy
5. The antibonding orbitals are less stable and higher in energy
6. We fill the molecular orbitals according to Pauli Exclusion Principle, i.e.
lower energy MOs are filled first
7. We fill the molecular orbitals according to Hund’s rule, i.e. electrons always
enter an empty orbital before they pair up

Note: you can construct the MO diagram, with or without non-valence electrons,
both are correct
Bond Order: the net contribution of the electrons to the bond strength of a molecule

𝟏𝟏
𝑩𝑩. 𝑶𝑶 = 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 − 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐
𝟐𝟐

The bond order does not need to be an integer number

 B.O. =1 ≡ one sigma bond
 B.O. =2 ≡ one sigma bond and one pi bond
 B.O. =3 ≡ one sigma bond and 2 pi bonds
Homonuclear diatomic molecules with MOs originating from s orbitals
 Bring Two Hydrogen Atoms Together

H2 molecule is more stable than individual H atoms.

B.O=1 1 sigma bond.

𝟏𝟏 𝟏𝟏
𝑩𝑩. 𝑶𝑶 = 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 − 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 = (𝟐𝟐 − 𝟎𝟎) = 𝟏𝟏
𝟐𝟐 𝟐𝟐
 He Atoms

𝟏𝟏 𝟏𝟏
𝑩𝑩. 𝑶𝑶 = 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 − 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 = (𝟐𝟐 − 𝟐𝟐) = 𝟎𝟎
𝟐𝟐 𝟐𝟐

Does He2 molecule exist?

B.O=1 0 bond
 Li Atoms

Li Li
Be Atoms

Does Be2 Molecule exist?

Homonuclear diatomic molecules with MOs originating from s & p orbitals
Schematic of MO diagram from P orbitals
 Switch in 𝜎𝜎 and 𝜋𝜋 orbital ordering

Due to the stronger head-to-head overlaps of the orbitals, 𝜎𝜎 orbitals are usually more stable/lower in energy than
𝜋𝜋 orbitals. However, this is not always the case and sometimes there is a switch between the orbital ordering as shown in
the figure below what is the reason for that?

Z<8
 Switch in 𝜎𝜎 and 𝜋𝜋 orbital ordering

Due to the stronger head-to-head overlaps of the orbitals, 𝜎𝜎 orbitals are usually more stable/lower in energy than
𝜋𝜋 orbitals. However, this is not always the case and sometimes there is a switch between the orbital ordering as shown in
the figure below what is the reason for that?

Z<8
 B Atoms

incomplete
 C Atoms

𝟏𝟏
𝑩𝑩. 𝑶𝑶 = 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 − 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 =
𝟐𝟐
N Atoms
 O Atoms

B.O= sigma bond, pi bond.

𝟏𝟏
𝑩𝑩. 𝑶𝑶 = 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 − 𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆𝒆 𝒊𝒊𝒊𝒊 𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒂𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃𝒃 𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 =
𝟐𝟐
F Atoms
 What is the reason for that? Sp mixing

Due to the stronger head-to-head overlaps of the orbitals, 𝜎𝜎 orbitals are usually more stable/lower in energy
than 𝜋𝜋 orbitals. However, this is not always the case and sometimes there is a switch between the orbital
ordering what is the reason for that?

s-p mixing occurs when the s and p orbitals have similar energies for example 2s and 2p with a
tiny energy difference. s-p mixing does not generate new orbitals.
GAS LAWS: The ideal gas equation

PV = nRT

𝑷𝑷 𝑷𝑷𝑷𝑷 𝟑𝟑
𝑽𝑽(𝒎𝒎 ) = 𝐧𝐧 𝐦𝐦𝐦𝐦𝐦𝐦𝐦𝐦 𝐑𝐑 ? 𝐓𝐓(𝐊𝐊)
𝑷𝑷𝑷𝑷 𝒎𝒎𝟑𝟑 𝑱𝑱
𝑹𝑹 = 𝟖𝟖. 𝟑𝟑𝟑𝟑𝟑𝟑 −𝟏𝟏 −𝟏𝟏
=
(𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎) 𝑲𝑲 (𝒎𝒎𝒎𝒎𝒎𝒎𝒎𝒎)−𝟏𝟏 𝑲𝑲−𝟏𝟏
How to Determine the Intermolecular Forces of a Substance

Intramolecular Forces are the forces within the molecules or the covalent bonds between the atoms

Intermolecular Forces are attraction between molecules

1) London Dispersion

2) Dipole-Dipole

3) Hydrogen Bond

Determine if the compound is polar or non-polar

 Intermolecular Forces of Polar and Non-polar compound

Non-polar compound Polar compound

London Dispersion London Dispersion

There is no lone pair on the central atom Dipole-dipole

The atoms around the central atom are the same If H is directly attached to F-O-N
Then there is H-bonding as well.
 Intermolecular Forces of Polar and Non-polar compound

CO2 is non-polar: London dispersion CH3NH2 has N and H next to each other, thus,
London dispersion, Dipole-dipole, H-bonding
No lone pair on the central atom and both surrounding
atoms are Oxygen CH5H12 any compound with C and H only is non-
polar thus, London dispersion
SF4 is polar: London dispersion and
HCl polar, London dispersion and Dipole/dipole
Dipole-dipole

lone pair on the central atom and both surrounding

atoms are Oxygen
 Which Compound has a higher boiling point

Boiling process is liquid-to gas-conversion, we have to break the intermolecular attraction. Thus,
Molecules with stronger intermolecular forces have a higher boiling point.

London dispersion Hydrogen bonding Ion-ion

Dipole-dipole Ion dipole

London dispersion Hydrogen bonding Ion-ion

Dipole-dipole Ion dipole

HCl and HF, HF has hydrogen bonding. HF KOH and H2O, ionic compound vs H bonding
KOH
CO2 and OCS, CO2 is non-polar (LDF), and OCS is
polar no lone-pair but it is non-symmetrical. D/D
interaction. OCS

C5H12 and C2H4, C and H only! Non polar, only LDF.

The larger molecule has the stronger LDF. C5H12

CH3OH and CH2O, H bonding vs. DD. CH3OH