Introduction to FMO Theory
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Transcript of Introduction to FMO Theory
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Introduction to FMO Theory
AO. AO
MO*
MO
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LUMOHOMO
LUMO
HOMO
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Introduction to FMO Theory
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• No net stabilization
Net Stabilization
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ΔE
HOMO
LUMO
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hν
LUMO
HOMO
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hν
LUMO
HOMO
SOMO
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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
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Electrocyclic Reactions
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Example
Me
Me
Me
Me
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Me
Me LUMO
HOMO
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LUMO
HOMO
E
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LUMO
HOMO
E
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LUMO
HOMO
E
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Me
Me
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Me
Me
HOMO
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Me
Me
HOMO
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Me
Me
HOMO
Orbitalmatch
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Me
Me
HOMO
Orbitalmatch
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Me
Me LUMO
HOMO
Orbitalmatch
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Me
Me
Me
Me
LUMO
HOMO
Orbitalmatch
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Me
Me LUMO
HOMO
Orbitalmatch
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Me
MeMe
Me
Δ
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Me
Me
Me
Me
hν
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ψ4
ψ3
ψ2
ψ1
Me
MeLUMO
HOMOHOMO
LUMO
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Me
Me Me
Me
HOMO
LUMO
hν
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Cycloaddition Reactions
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Cycloaddition Reactions
LUMOSHOMOS
HOMORLUMOR
I
n
n'k'
k
m
m'I'
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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
+
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[2+2] cycloaddition
• Can you react two ethylene molecules by thermal conditions?
Heat +
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Orbital Analysis of [2+2]Cycloaddition Reaction
NoMatch
Match
Molecule 1 Molecule 2
LUMO
HOMO
LUMO
HOMO
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SOMO*
hν
LUMO
HOMO
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SOMO*
hν
LUMO
HOMO
LUMO
HOMO
1 2Molecule Molecule
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SOMO*
hν
LUMO
HOMO
LUMO
HOMO
1 2Molecule Molecule
Match
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Regiochemical Predictions
O-Me O-Me O-MeMe-O Me-O
O-Me
and / orhν
+
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CH 2- O-Me
• •
ψ1 ψ1
hνHOMO ψ2 ψ2
SOMO* ψ3ψ3LUMO
as a model for
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