What is Molecular Orbital Theory?

• Scientists choose the model that best helps them answer a particular
question

• If we want to know shape, use VSEPR along with Valence-Bond and Hybrid-
Orbital Theories

• But, VB doesn’t explain magnetic & spectral properties and only considers
localized electron density

• MO theory considers the TOTAL electron densities and bonding properties

according to symmetry (constructive and destructive orbital overlaps)

• In MO theory, the molecule is described as a collection of nuclei with the

electron orbitals delocalized over the entire molecule
 How does it work?
• Key ideas: formation of MOs from AOs, energy and shape of MOs and how they are
populated by electrons
• Approximations are used: Mathematically combine (add or subtract) the atomic
orbitals (specifically, the atomic wave functions) of nearby atoms to form MOs
(molecular wave functions)
• Addition of two wavefunctions gives a bonding MO (increases probability of finding
electrons between the nuclei giving a bond)
• Subtraction of two wavefunctions gives an antibonding MO (decreases probability of
finding electrons between two nuclei to zero, a node)
• This means number of MOs will always be the same as the number of AOs
• Bonding MOs are lower in energy than their antibonding MOs
• AOs must be of similar energy and orientation (the symmetry)
• Bonding and antibonding MOs most commonly combine in two types of symmetry, σ
(sigma) and π (pi) bonds
• Electrons fill Mos just as they do AOs, following Aufbau, Pauli and Hund
• MOs are best represented in a Molecular Orbital Diagram
• The MOs are labelled according to their bonding symmetry (σ or π) and the orbitals
from which they are made (1s, 2p 3d etc.)
• Antibonding orbitals are denoted by a superscript star (*)

Eg. 1s1 + 1s1 = (σ1s)2 1s1 – 1s1 = (σ1s*)2

MO Diagrams of 2nd Period Diatomics
Do not memorize these
 MO diagram for He2+ and He2.

σ*1s σ*1s
Energy

Energy
1s 1s 1s 1s

σ1s σ1s
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He

He2+ bond order = He2 bond order =

SAMPLE PROBLEM Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

PLAN: Use H2 as a model and accommodate the number of electrons in

bonding and antibonding orbitals. Find the bond order.

SOLUTION:
bond order: bond order:

σ∗ σ∗

1s 1s 1s 1s

AO of H AO of H AO of H-
AO of H
σ σ configuration is:
configuration is:
MO of H2+ MO of H2-
 Bonding in s-block homonuclear diatomic molecules.

σ*2s
Energy

σ*2s

2s 2s 2s
2s

σ2s σ2s

Li2 Be2
Li2 bond order = Be2 bond order =
Contours and energies of s and p MOs through
combinations of 2p atomic orbitals.
Relative MO energy levels for Period 2 homonuclear diatomic molecules.

without 2s-2p with 2s-2p

mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2
MO occupancy
and molecular
properties for B2
through Ne2
The paramagnetic
properties of O2
 SAMPLE PROBLEM Using MO Theory to Explain Bond Properties

PROBLEM: As the following data show, removing an electron from N2 forms

an ion with a weaker, longer bond than in the parent molecules,
whereas the ion formed from O2 has a stronger, shorter bond:
N2 N2+ O2 O2+
Bond energy (kJ/mol) 945 841 498 623
Bond length (pm) 110 112 121 112

Explain these facts with diagrams that show the sequence and occupancy of MOs.

PLAN: Find the number of valence electrons for each species, draw the MO
diagrams, calculate bond orders, and then compare the results.

SOLUTION:
N2 has 10 valence electrons, so N2+ has 9.

O2 has 12 valence electrons, so O2+ has 11.

 SAMPLE PROBLEM Using MO Theory to Explain Bond Properties

N2 N2+ O2 O2+
σ∗2p σ∗2p

π∗2p π∗2p

σ2p π2p
π2p σ2p

σ∗2s σ∗2s

σ2s σ2s
bond
orders:
 The MO diagram for HF
σ∗
Energy

1s

2px 2py 2p

σ
2s
AO of H MO of HF AO of F
 σ*2p The MO diagram for CO

π*2p
2p
Energy

σ2p
2p possible Lewis
structures
π2p
-1 +1

C O
σ*2s
2s
2s
AO of C
AO of O
σ2s
MO of CO
 σ*2p The MO diagram for NO

π*2p

2p
Energy

σ2p 2p
possible Lewis
structures
π2p
0 0
N O
σ*2s
-1 +1
2s N O
2s
AO of N
AO of O
σ2s
MO of NO