one inorganic chem

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Chem 404

California State University San Marcos

CHEM

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Molecular Orbitals Molecular Orbitals from Linear Combination of Atomic Orbitals 1. Conservation of orbitals Total # of atomic orbitals = total # of resulting molecular orbitals 2. Linear combination: addition or subtraction of wavefunctions 3. Addition: constructive interference Subtraction: destructive interference See H2 as an example Molecular Orbital Diagram for H2 How About a Theoretical He2 Molecule? Molecular Orbital Diagram for He2 Bond Order Bond order = (# of e in bonding orbital - # of e in antibonding orbital) / 2 Bond order = 1 Bond order = 0 Molecular Orbitals originated from p orbitals Molecular Orbital Diagram for O2 and F2 O2 F2 2p 2p 2s 2s 2p 2p 2s Bond orders? How about O2+, O2-, and O22- 2s Symmetry-Allowed Orbital Mixing σ∗ σ∗ 2p 2p σ σ σ∗ 2s σ 2p 2p σ∗ 2s 2s 2s σ Orbital Mixing N2 σ∗ σ∗ π∗ Lowest unoccupied molecular orbital (LUMO) π∗ 2p 2p 2p 2p Highest occupied molecular orbital (HOMO) σ σ π π σ∗ 2s σ∗ 2s σ 2s 2s σ Where Orbital Mixing is Significant σ∗ π∗ 2p 2p σ Li2 Be2 B2 C2 N2 O2 π F2 σ∗ 2s 2s σ g for gerade: orbital has an i u for ungerade: orbital doesn’t have an i Ne2 Heteronuclear Diatomic Molecules HF One general tip: orbitals on more electronegative atoms are lower in energy Take HF as an example σ∗ 1s 2p σ 2s Heteronuclear Diatomic Molecules: CO σ∗ π∗ 2p σ 2p π σ∗ 2s σ 2s
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