Molecular Orbital Theory

Describes bonding in molecules using linear combinations of atomic orbitals (LCAO) to form molecular orbitals

Bond Order Formula

Bond Order = (nb - na) / 2

nb = Bonding Electrons

Number of electrons in bonding molecular orbitals

na = Antibonding Electrons

Number of electrons in antibonding orbitals (marked with *)

Key Principles

1. Orbital Combination

Atomic orbitals combine to form molecular orbitals: same number of MOs as AOs

2. Bonding Orbitals (σ, π)

Lower energy than atomic orbitals; constructive interference; electron density between nuclei

3. Antibonding Orbitals (σ*, π*)

Higher energy; destructive interference; node between nuclei; destabilizes molecule

4. Aufbau Principle

Fill lowest energy MOs first; Hund's rule applies; Pauli exclusion principle

MO Energy Level Order

For O₂, F₂, Ne₂

σ(2s) < σ*(2s) <

σ(2p) < π(2p) <

π*(2p) < σ*(2p)

For B₂, C₂, N₂

σ(2s) < σ*(2s) <

π(2p) < σ(2p) <

π*(2p) < σ*(2p)

Note: π and σ(2p) order switches

Worked Examples

Example 1: O₂ Molecule

Total electrons: 8 + 8 = 16

Configuration:

σ(2s)² σ*(2s)² σ(2p)² π(2p)⁴ π*(2p)²

Bond Order Calculation:

Bonding electrons (nb) = 2+2+4 = 8

Antibonding electrons (na) = 2+2 = 4

Bond Order = (8-4)/2 = 2

Result: Double bond, paramagnetic (2 unpaired e⁻)

Example 2: N₂ Molecule

Total electrons: 7 + 7 = 14

Configuration:

σ(2s)² σ*(2s)² π(2p)⁴ σ(2p)²

Bond Order:

nb = 2+4+2 = 8

na = 2

Bond Order = (8-2)/2 = 3

Result: Triple bond, diamagnetic, very stable

Example 3: He₂ (Does not exist)

Total electrons: 2 + 2 = 4

Configuration: σ(1s)² σ*(1s)²

Bond Order:

Bond Order = (2-2)/2 = 0

Result: No bond formation; He₂ does not exist

Bond Order Interpretation

Bond OrderBond TypeStabilityExample
0No bondUnstableHe₂
0.5Weak bondMarginally stableHe₂⁺
1Single bondModerateH₂, F₂
2Double bondStrongO₂
3Triple bondVery strongN₂

Note: Higher bond order → shorter bond length and higher bond energy

Common Mistakes

⚠️

Wrong MO Energy Order

Remember π(2p) and σ(2p) switch order for B₂, C₂, N₂

⚠️

Forgetting Antibonding Electrons

Must subtract antibonding electrons when calculating bond order

⚠️

Ignoring Hund's Rule

Fill degenerate π orbitals singly before pairing (affects paramagnetism)

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Paramagnetic vs Diamagnetic

Unpaired electrons → paramagnetic; all paired → diamagnetic