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3-MO Theory PDF
3-MO Theory PDF
Valence Bond Theory: Electrons are located in discrete pairs between specific atoms
Thus the main difference between these theories is where the electrons are located,
in valence bond theory we predict the electrons are always held between two bonded atoms
and in molecular orbital theory the electrons are merely held “somewhere” in molecule
ΨMOL
=
c1
φ1
+
c2
φ2
+
c3
φ3
+
cn
φn
If the ΨMOL can be determined, then where the electrons are located can also be determined
66
Building Molecular Orbitals from Atomic Orbitals
Similar to a wave function that can describe the regions of space where electrons reside on
time average for an atom, when two (or more) atoms react to form new bonds, the region
where the electrons reside in the new molecule are described by a new wave function
This new wave function describes molecular orbitals instead of atomic orbitals
Hydrogen 1s
H-H bonding
atomic orbital
molecular orbital
67
Building Molecular Orbitals from Atomic Orbitals
In the case of H2, in addition to the new bonding molecular orbital obtained by adding the two
atomic 1s orbitals, an antibonding orbital is obtained by subtracting the two atomic orbitals
node
H-H antibonding
molecular orbital
68
Electronic Configuration for H2
Eσ* > Eσ
-due to electron repulsion
X Y X Y X Y X Y
Thus for the only filled orbital in H2, because the molecule is symmetric |C1| = |C2|
Also if all the MOs are filled, there must be one electron in each spin state on each atom
The electron location in H2 is identical between valence bond theory and molecular orbital theory
(due to there only being one bond in H2 and thus the electrons must be located on the two atoms)
What happens however if there is more than one bond in the molecule,
how do the bonding theories differ in describing the location of electrons?
Consider methane
2p
sp3
hybridization
energy
2s
1s
1s
Each sp3 hybridized orbital would thus form a
bond with the 1s orbital from each hydrogen to
form four identical energy C-H bonds
72
Molecular Orbital Theory
H 1s
C 2s
C 2px
C 2py
C 2pz
Then mix the outer shell atomic orbitals to find the bonding patterns
0 nodes
1 node
1 node
1 node
Molecular orbital theory predicts there are 4 bonding MOs, 1 with 0 nodes and 3 with 1 node
(therefore they must be at different energy levels if different number of nodes!)
74
Molecular Orbital Theory
The bonding pattern in methane is thus different using either valence bond
or molecular orbital theory
Inner shell C 1s
Inner shell C 1s
Each sp3 hybridized orbital would thus form a The bonding MOs for methane would not
bond with the 1s orbital from each hydrogen to be of identical energy
form four identical energy C-H bonds
0 nodes
1 node
1 node
1 node
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Chem. Phys. Lett. (1968), 613-615
Molecular Orbital Theory
Using molecular orbital theory therefore the electrons are located in regions of space
on time average (orbitals) that are formed by the mixing of atomic orbitals
Eσ*
Eσ
When forming molecular orbitals of H2 from atomic orbitals from each hydrogen atom,
hydrogen only has one electron in a 1s orbital (or a 1,0,0 orbital using n,l,m designation)
When building molecular orbitals from a 2nd row atom (like carbon) can use
either the 2s (2,0,0) or 2p (2,1,-1; 2,1,0; or 2,1,1) atomic orbitals to form the bonds
When different orbitals interact, the overlap of the orbitals changes depending upon the
direction of bond formation (both in degree of overlap and symmetry of the bond)
When two s orbitals interact, due to When two p orbitals interact, if lobe with
symmetry of orbital the direction of approach same phase is pointing toward each other a
is irrelevant
bonding region can occur
When two molecules react (each with their own set of molecular orbitals) it is important to
recognize which molecular orbital interaction determines the reaction
(if a chemist knows this then they can predict reactions)
The amount of energy gain is also dependent upon how close in energy
the two orbitals are before mixing
Consider mixing of two orbitals, one filled (OMO) and one unfilled (UMO)
ΔE
ΔE
If the OMO is identical in energy to the As the OMO has a greater difference in
UMO there will be the maximum energy gain energy to the UMO, the mixing will be less
due to the best possible mixing of the orbitals
and the energy gain will thus be lower
Thus the energy gain is greatest in a reaction when the HOMO of one compound
is closest in energy to the LUMO of the second compound
83
Building New Molecular Orbitals from Molecular Orbitals
When mixing any two orbitals therefore the two important considerations are the overlap
between the two orbitals and the match in energy of the two orbitals before mixing
Considerations between mixing of orbitals are therefore:
-when two nonorthogonal orbitals overlap and mix, they generate two new orbitals
(one higher in energy and one lower in energy)
-the amount of energy shift upon mixing is greater with more overlap of the orbitals and
lower the further apart in energy the orbitals are before mixing
-average energy of two new orbitals is slightly higher than average of original orbitals
(partly an artifact of electron-electron repulsion in higher energy orbital)
Since the majority of energy gain in a reaction between two molecules is a result of the
HOMO of one molecule reacting with the LUMO of a second molecule this interaction is
called a Frontier Molecular Orbital (FMO) interaction
A reaction is thus favored when the HOMO (nucleophile) is unusually high in energy
and the LUMO (electrophile) is unusually low in energy
If the HOMO of a new compound is higher in energy than the HOMO of the C-H bond,
then it will be more reactive as a nucleophile
If the LUMO of a new compound is lower in energy than the LUMO of the C-H bond,
then it will be more reactive as an electrophile
How much higher or lower in energy will determine the relative rates of reactions
85
Frontier Molecular Orbital Theory
CH3
sp3C
1s H
H+
OH
:NH3
:OH2
σC-H
Very low HOMO,
Factors that can adjust MO energy levels:
therefore poor nucleophile
1) Unmixed valence shell atomic orbitals
A sp3 hybridized carbon atom and a 1s
orbital of hydrogen have similar 2) Electric charge
energy levels and strong overlap,
87
therefore high mixing
Frontier Molecular Orbital Theory
2p O
πC-O
σC-H
Very low HOMO,
Factors that can adjust MO energy levels:
therefore poor nucleophile
1) Unmixed valence shell atomic orbitals
A sp3 hybridized carbon atom and a 1s
orbital of hydrogen have similar 2) Electric charge
energy levels and strong overlap, 3) Poor overlap of atomic orbitals
89
therefore high mixing
4) Poor energy match of orbitals
Frontier Molecular Orbital Theory
Frontier molecular orbital (FMO) theory allows a chemist to make predictions about a
reaction by knowing the placement of the HOMO and LUMO energy levels
A high HOMO level represents a compound that is a good nucleophile
Anything that will raise
CH3 > NH2 > OH energy level of HOMO will
increase nucleophilicity
The energy level of the HOMO and LUMO can be predicted by knowing
that when two atomic orbitals mix they form two new molecular orbitals,
one lower in energy and one higher in energy
The amount of mixing is dependent upon:
1) The amount of overlap between the mixing orbitals
(e.g., the overlap for a σ bond is greater than the overlap for a π bond)
2) The closer in energy are two orbitals, the greater the amount of mixing that occurs
91
Frontier Molecular Orbital Theory
FMO will also allow prediction about where a reaction will occur (regiochemistry)
and direction of approach (stereochemistry)
FMO predicts that a carbonyl should react as an electrophile due to the low energy LUMO
LUMO of
formaldehyde
92
Frontier Molecular Orbital Theory
What direction should a nucleophile approach the carbonyl?
NUC
NUC
Direction appears better,
Optimal interaction
but still not optimal interaction
(best overlap of
interacting orbitals)
NUC
Expect this direction to be highly
disfavored due to orthogonal
interaction with orbitals
Could there possibly be a method to test the angle of approach of nucleophile to carbonyl?
Since alkyl halide is reacting as the electrophile, need to look at the LUMO
Largest coefficient is on the
backside of the carbon
Nucleophile thus reacts with a
NUC methyl halide in a SN2 reaction
with backside attack
So called “inversion of
configuration”
LUMO of methyl halide
Bonds that break
base
Base thus reacts by abstracting
hydrogen anticoplanar to
The base will abstract the leaving group and form new π
hydrogen that is anticoplanar
bond in E2 reaction
to leaving group
New π bond
LUMO of 2˚ alkyl halide
95