Paramagnetic species- contain one or more unpaired electrons, are attracted to magnet

fields.

o The Lewis structure for O2 shows no unpaired electrons.O2 exhibits paramagnetism

https://youtu.be/KcGEev8qulA?t=23
5.7 Molecular Orbital (MO) Theory
• In molecular orbital (MO) theory, the atomic orbitals of ALL atoms in the molecule
are combined to make new molecular orbitals that are delocalized over the entire
molecule.
• Recall that atomic orbitals are wave functions (Ψ).
• Plotting Ψ2 in Cartesian coordinates gives the shapes of the atomic orbitals.

• Molecular orbitals have characteristics similar to atomic and hybrid orbitals:

✓ specific shapes
✓ specific energies
✓ accommodate a maximum of 2 electrons each
✓ electron filling follows the Pauli exclusion principle, Hund’s rule and the
Aufbau’s Principle
✓ the number of molecular orbitals obtained equals the number of orbitals
combined
5.7 Molecular Orbital (MO) Theory
• Linear combination of atomic orbitals (LCAO)
- Technique used to construct molecular orbitals from atomic orbitals.
H2
o Localized Electron Model/Valence bond theory:
✓ H2 forms from the overlap of the 1s orbitals.

o Molecular orbital theory:

✓ H2 forms when the 1s orbitals combine to give molecular orbitals.
5.7 Molecular Orbital (MO) Theory
Constructing molecular orbitals: Usable AOs are usually the valence orbitals on each atom.
Consider H2 molecule
1. Bonding Molecular orbital o Bonding molecular orbital is in energy
Valence orbitals of than the atomic orbitals
1S =
the isolated atoms o electron density between the nuclei.

o The * distinguishes an antibonding molecular orbital from a bonding orbital.

2. Antibonding molecular (*) orbital
o Antibonding molecular (*) orbital
Valence orbitals of
the isolated atoms *1S = is in energy than the
atomic orbitals.
o electron density, between
the nuclei.
5.7 Molecular Orbital (MO) Theory
Characteristics that can be explained using MO theory
1. Stability of the Diatomic molecule or ion.
No. of e− in bonding orbitals − No. of e− in antibonding orbitals
bond order =
2
• We will only consider valence electrons when we are calculating bond

• Higher bond order means and shorter bonds

• If bond order = 0, then bond is unstable compared to individual atoms and no bond will form.

2. Magnetism
• Diamagnetic - Substance with no unpaired electrons that is weakly repelled by a
magnetic field
• Paramagnetic- Substance with unpaired electrons that is attracted to a magnetic field
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules
Use molecular orbital theory to determine the bond order and whether the
ion/molecule is paramagnetic or diamagnetic

1. Determine the number of valence electrons in the molecule or ion.

2. Fill the orbitals beginning with the lowest energy orbital and progressing
upward until all electrons have been assigned to an orbital.

- two electrons (with paired spins) per orbital

- degenerate orbitals with single electrons (with parallel spins) before pairing.
5.7 Molecular Orbital (MO) Theory
Combine AOs to construct MOs.
• Principle of orbital conservation: The number of AOs combined must equal the number of
MOs formed.
• When n AOs combine to form n MOs, ANTIBONDING orbitals increase in energy,
BONDING orbitals decrease in energy.

Example: Period One Homonuclear Diatomic Molecules

molecular orbitals
1. H2
*1S

1s 1s
2 − 0
bond order = = 1 H H
2 atomic orbital
 atomic orbital
1S
Paramagnetic or diamagnetic? H2-
The molecular orbital electron configuration forH2 is(σ1s) 2
4
5.7 Molecular Orbital (MO) Theory
Example: Period One Homonuclear Diatomic Molecules
2. H -
2

1s* Paramagnetic or diamagnetic?

1s
1s
H- H
1s
H2-

No. of e− in bonding orbitals − No. of e− in antibonding orbitals

bond order =
2
2 −1 1
Bond order = =
12 2
-
According to molecular orbital theory, H2

The molecular orbital electron configuration for H2- is (1s)2 (1s*)1

5.7 Molecular Orbital (MO) Theory
Example: Period One Homonuclear Diatomic Molecules
3. He2

1s*
1s 1s

He 1s He
He2

No. of e − in bonding orbitals − No. of e− in antibonding orbitals

bond order =
2
2 12 1
Bond order = = 0
12 2

According to molecular orbital theory, He2 is a stable molecule and

does exist.
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules Period 2 (valence electrons are
located at n=2: 2s 2p)

a) Li2
b) Be2 – does not exist
c) B2
d) C2
e) N2 P block
f) O2
g) F2
h) Ne2 – does not exist
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules
4. Be2

2s**
2s 2s
Be Be
2s
Be2

No. of e− in bonding orbitals − No. of e− in antibonding orbitals

bond order =
2
2 2
bond order = =0
2
According to molecular orbital theory, Be2
5.7 Molecular Orbital (MO) Theory
Interaction of p Orbitals

σ molecular
orbitals from px
atomic orbitals

2 π molecular
orbitals orbitals
from py and pz
atomic orbitals
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules

molecular orbitals molecular orbitals

B2, C2, and N2 O2, F2

*2p *2p
*2p *2p
2p 2p
Flipped! 2p
2p
*2s
*2s
2s
2s
5.7 Molecular Orbital (MO) Theory

• Bond dissociation energy (BDE, D) - the energy required for homolytic bond
cleavage (i.e., the breaking a bond so that bonding electrons are distributed equally).
• Bond breaking is always an endothermic process; therefore, BDE-values (D) are
always positive.

BDE

Review:
• π bonds are weaker than σ bonds because they result from less efficient side- on
overlap of unhybridized p orbitals (i.e., the π bonds share electrons less efficiently
than σ bonds).
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules

• order of the  and  molecular orbitals in B2, C2, N2 is flipped!

• Higher bond order meanshigher bond energy and bond length!
5.7 Molecular Orbital (MO) Theory
Example: Period Two Homonuclear Diatomic Molecules
How many molecules below do not exist?
a. 0
b. 1
c. 2
d. 3
e. 4
5.7 Molecular Orbital (MO) Theory
Example: Period Two Heteronuclear Diatomic Molecules

Heteronuclear Diatomic Molecules and Ions

• Two different atoms
• Combination of “identical” AO results in equal contribution from both AO to the MO.
• However, for AOs with different energies and types, the AO closest to the MO
contributes the most.
• More electronegative atoms have lower energy (nrg) orbitals
• Lower nrg AOs contribute more to bonding MOs
• Higher nrg AOs contribute more to antibonding MOs
5.7 Molecular Orbital (MO) Theory
Example: Period Two Heteronuclear Diatomic Molecules
Partial MO energy-level diagram Electron probability distribution

• The fluorine 2p orbital is lower in energy than the hydrogen 1s orbital

-The σ MO closer to fluorine 2p
• Electron pairs are not equally shared
5.7 Molecular Orbital (MO) Theory
Example: Period Two Heteronuclear Diatomic Molecules
Use the molecular orbital model to predict the magnetism and bond order of the CN– ions

▪ CN– ion also has valence *2p

electrons (4 + 5 + 1)
*2p
2p
▪ 8–2 =3 2p
8 –2 2
=3
Bond order = 2

The molecular orbital electron configuration is

Paramagnetic or diamagnetic?
5.7 Molecular Orbital (MO) Theory

Key Points
The VSEPR Model Bonding Molecular Orbitals
Electron Domain Geometry Antibonding Molecular Orbitals
Molecular Geometry Bond Order
Bond Angles Molecular Orbital Diagrams
Axial and Equatorial
Molecular Polarity
Valence Bond Theory
Hybridization
Sigma Bonds
Pi Bonds
Bond rotation
Molecular Orbital Theory