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M 1
M 1
1s + 1s
1 2
A ------ B
Each MO may be written as an LCAO: c11 c22
Since the probability density is given by the square of the wavefunction:
c c
1 1 2 2 c c
1
2
2
2
d 1
_ d 1 ):
2 2
After normalization (setting and
1 1
(1 2 ) (1 2 )
[2(1 S )]1/2
[2(1 S )]1/2
∆E2
Energy
∆E1
Ha H-H Hb
• ∆E2 > ∆E1, so the antibonding orbital is always more anti-bonding than the bonding
orbital is bonding
MOs for H2
1
• in phase combination
2
(12 22 212 )
• constructive interference 2(1 S )
• large e- density in the internuclear region (bonding)
• an electron in this MO lowers the molecule’s energy
1
• out of phase combination
2
(12 22 212 )
• destructive interference 2(1 S )
• small e- density in the internuclear region (antibonding)
• nodal plane between atoms
• an electron in this MO raises the molecule’s energy
MO Notation
1 2
E E
H2 vs. He2
dihydrogen dihelium
1
BO # bonding e # anti-bonding e
2
Basic Rule #2 of MO Theory
Rule #2: If the AOs are degenerate, their interaction is
proportional to their overlap integral, S.
1 2 1 2
large overlap small overlap
S=0 S=0
Overlap and Symmetry
1s/2p overlap depends on the angle θ:
θ = 90° θ = 0°
S 1s/2p
S=0
Overlap and Symmetry
d orbitals zero overlap by
symmetry
sigma
pi
delta
Basic Rule #4 of MO Theory
Rule #4: If the AOs are non-degenerate, their interaction is
proportional to S2/ΔE, where ΔE is the energy separation
between the AOs. In this case the bonding orbital is mostly
localized on the atom with the deeper lying AO, usually the
more electronegative atom. The antibonding orbital is mostly
localized on the atom with the higher AO.
c11 c22
c c
2
1
2
2
1
2
Orbitals with ΔE > 12-14 eV have essentially zero interaction.
Basic Rule #4 of MO Theory
strong
interaction
bonding and
antibonding
weak
interaction
almost
nonbonding