Introduction to FMO Theory
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Transcript of Introduction to FMO Theory
Introduction to FMO Theory
AO. AO
MO*
MO
LUMOHOMO
LUMO
HOMO
Introduction to FMO Theory
• No net stabilization
Net Stabilization
ΔE
HOMO
LUMO
hν
LUMO
HOMO
hν
LUMO
HOMO
SOMO
σ*s-s
σ s-s
+σ*p-p
σ p-p
+σ*sp3-sp3
σsp3-sp3
+σ*s-sp 3
σs-sp 3
+
+
π*p-p
πp-p
Electrocyclic Reactions
Example
Me
Me
Me
Me
Me
Me LUMO
HOMO
LUMO
HOMO
E
LUMO
HOMO
E
LUMO
HOMO
E
Me
Me
Me
Me
HOMO
Me
Me
HOMO
Me
Me
HOMO
Orbitalmatch
Me
Me
HOMO
Orbitalmatch
Me
Me LUMO
HOMO
Orbitalmatch
Me
Me
Me
Me
LUMO
HOMO
Orbitalmatch
Me
Me LUMO
HOMO
Orbitalmatch
Me
MeMe
Me
Δ
Me
Me
Me
Me
hν
ψ4
ψ3
ψ2
ψ1
Me
MeLUMO
HOMOHOMO
LUMO
Me
Me Me
Me
HOMO
LUMO
hν
Cycloaddition Reactions
Cycloaddition Reactions
LUMOSHOMOS
HOMORLUMOR
I
n
n'k'
k
m
m'I'
The Mathematical Basis of Cycloaddition Predictions
SE = 2(l.k + l' .k') 2 . β2
α( )HOMO S - α( )LUMO R α( )HOMO R - α( )LUMO S
2(m. + n m'. )n' 2 .β2
+
[2+2] cycloaddition
• Can you react two ethylene molecules by thermal conditions?
Heat +
Orbital Analysis of [2+2]Cycloaddition Reaction
NoMatch
Match
Molecule 1 Molecule 2
LUMO
HOMO
LUMO
HOMO
SOMO*
hν
LUMO
HOMO
SOMO*
hν
LUMO
HOMO
LUMO
HOMO
1 2Molecule Molecule
SOMO*
hν
LUMO
HOMO
LUMO
HOMO
1 2Molecule Molecule
Match
Regiochemical Predictions
O-Me O-Me O-MeMe-O Me-O
O-Me
and / orhν
+
CH 2- O-Me
• •
ψ1 ψ1
hνHOMO ψ2 ψ2
SOMO* ψ3ψ3LUMO
as a model for