HOMO-LUMO ("filled-empty") Orbital Interactions

A fundamental principle: all steps of all heterolytic

reaction mechanisms are either Bronsted or Lewis
acid-base reactions

They involve either proton transfer (Bronsted), or

unshared pair/empty orbital interactions (Lewis).
When the interacting atomic orbitals are
considered, the Bronsted reactions can be seen
as simply a special case of the Lewis, in which
the empty orbital is the antibonding orbital of the
H-X bond.

In short, all heterolytic reactions are just examples of

interactions between filled atomic or molecular
orbitals and empty atomic or molecular orbitals - that
is, Lewis acid-base reactions. Here is a diagram to
explain this point:

The interaction of any two atomic or molecular

orbitals, as you learned in general chemistry,
produces two new orbitals.

One of the new orbitals is higher in energy than

the original ones (the antibonding orbital), and
one is lower (the bonding orbital).
When one of the initial orbitals is filled with a pair
of electrons (a Lewis base), and the other is
empty (a Lewis acid), we can place the two
electrons into the lower energy of the two new
orbitals.
The "filled-empty" interaction therefore is
stabilizing.

When we are dealing with interacting molecular

orbitals, the two that interact are generally

The highest energy occupied molecular orbital

(HOMO) of one molecule,
The lowest energy unoccupied molecular orbital
(LUMO) of the other molecule.
These orbitals are the pair that lie closest in
energy of any pair of orbitals in the two
molecules, which allows them to interact most
strongly.
These orbitals are sometimes called
the frontier orbitals, because they lie at the
outermost boundaries of the electrons of the
molecules.

Here is the filled-empty interaction redrawn as a

HOMO-LUMO interaction.

Let's look at some examples. First, a reaction that you

would have categorized as a Lewis acid-base reaction
when you were studying general chemistry:

NH3 has an unshared pair on nitrogen, occupying the

HOMO (it is generally true that unshared pairs occupy
HOMOs). BH3 has an empty valence orbital on B,
since B is a Group II element. This is the LUMO.
Here are pictures of the two orbitals from AM1 semiempirical molecular orbital calculations:
NH3 HOMO

BH3 LUMO

The HOMO-LUMO energy diagram above describes

the formation of a bond between N and B.
Now let's try a slightly more complex case. Here's a
typical Bronsted acid-base reaction:

The curly arrows track which bonds are made, and

which are broken, but they do not indicate what
orbitals are involved.

Water is both a Bronsted base (capable of

accepting a proton) and a Lewis base, with one
of its unshared pairs (the HOMO).
H-Cl is a Bronsted acid, capable of donating a
proton, but it also is a Lewis acid, using the *
orbital of the H-Cl bond (the LUMO).

Here are pictures of the relevant HOMO and

LUMO, again from AM1 semi-empirical molecular
orbital calculations:
H2O HOMO

HCl LUMO

The interaction stabilizes the unshared pair of the

oxygen, while simultaneously breaking the H-Cl
bond because the interaction is with the
antibonding orbital.

Another example is the SN2 reaction, which involves

the HOMO of the nucleophile and the * orbital of the
R-X bond:

Here are the relevant orbitals:

OH- HOMO

CH3-Cl LUMO

The interaction stabilizes the unshared pair of the

oxygen, while simultaneously breaking the CH3-Cl
bond because the interaction is with the antibonding
orbital.
Other examples include the reaction of alkenes with
H-X, where the HOMO is the MO of the alkene and
the LUMO is the H-X * orbital:

and the capture of the carobcation in an SN1 reaction

by nucleophile:

You should need no reminder that the carbocation is

stabilized by a filled-empty interaction between the
empty p orbital of the positive carbon and the orbital
of an adjacent C-H or C-C bond
In short, all heterolytic reactions proceed because the
energy of a pair of electrons is lowered by the
interaction of a filled atomic or molecular orbital with
an empty one.
The same reasoning can be appllied to bimolecular
pericyclic reactions like the Diels-Alder cycloaddition.
This page last modified 3:24 PM on Thursday September 30th, 2010.
Webmaster, Department of Chemistry, University of Maine, Orono, ME
04469