Linear combinations of atomic orbitals (LCAO)[edit]

Main article: Linear combination of atomic orbitals

Molecular orbitals were first introduced by Friedrich Hund[2][3] and Robert S. Mulliken[4][5] in
1927 and 1928.[6][7] The linear combination of atomic orbitals or "LCAO" approximation for
molecular orbitals was introduced in 1929 by Sir John Lennard-Jones.[8] His ground-breaking
paper showed how to derive the electronic structure of thefluorine and oxygen molecules
from quantum principles. This qualitative approach to molecular orbital theory is part of the
start of modern quantum chemistry. Linear combinations of atomic orbitals (LCAO) can be
used to estimate the molecular orbitals that are formed upon bonding between the
molecule's constituent atoms. Similar to an atomic orbital, a Schrdinger equation, which
describes the behavior of an electron, can be constructed for a molecular orbital as well.
Linear combinations of atomic orbitals, or the sums and differences of the atomic
wavefunctions, provide approximate solutions to the HartreeFock equations which
correspond to the independent-particle approximation of the molecular Schrdinger
equation. For simple diatomic molecules, the wavefunctions obtained are represented
mathematically by the equations

where

and

are the molecular wavefunctions for the bonding and antibonding

molecular orbitals, respectively,

and

are the atomic wavefunctions from

atoms a and b, respectively, and

and

are adjustable coefficients. These

coefficients can be positive or negative, depending on the energies and symmetries

of the individual atomic orbitals. As the two atoms become closer together, their
atomic orbitals overlap to produce areas of high electron density, and, as a
consequence, molecular orbitals are formed between the two atoms. The atoms are
held together by the electrostatic attraction between the positively charged nuclei
and the negatively charged electrons occupying bonding molecular orbitals. [9]

Bonding, antibonding, and nonbonding MOs[edit]

When atomic orbitals interact, the resulting molecular orbital can be of three types:
bonding, antibonding, or nonbonding.
Bonding MOs:

Bonding interactions between atomic orbitals are constructive (in-phase)

interactions.

Bonding MOs are lower in energy than the atomic orbitals that combine to
produce them.

Antibonding MOs:

Antibonding interactions between atomic orbitals are destructive (out-of-phase)

interactions, with a nodal plane where the wavefunction of the antibonding
orbital is zero between the two interacting atoms

Antibonding MOs are higher in energy than the atomic orbitals that combine to
produce them.

Nonbonding MOs:

Nonbonding MOs are the result of no interaction between atomic orbitals

because of lack of compatible symmetries.

Nonbonding MOs will have the same energy as the atomic orbitals of one of the
atoms in the molecule.

Sigma and pi labels for MOs[edit]

The type of interaction between atomic orbitals can be further categorized by the
molecular-orbital symmetry labels (sigma), (pi), (delta), (phi), (gamma) etc.
paralleling the symmetry of the atomic orbitals s, p, d, f and g. The number of nodal
planes containing the internuclear axis between the atoms concerned is zero for
MOs, one for , two for , etc.
symmetry[edit]
For more details on this topic, see Sigma bond.
A MO with symmetry results from the interaction of either two atomic s-orbitals or
two atomic pz-orbitals. An MO will have -symmetry if the orbital is symmetrical with
respect to the axis joining the two nuclear centers, the internuclear axis. This means
that rotation of the MO about the internuclear axis does not result in a phase
change. A * orbital, sigma antibonding orbital, also maintains the same phase when
rotated about the internuclear axis. The * orbital has a nodal plane that is between
the nuclei and perpendicular to the internuclear axis.[10]
symmetry[edit]
For more details on this topic, see Pi bond.
A MO with symmetry results from the interaction of either two atomic px orbitals or
py orbitals. An MO will have symmetry if the orbital is asymmetrical with respect to

rotation about the internuclear axis. This means that rotation of the MO about the
internuclear axis will result in a phase change. There is one nodal plane containing
the internuclear axis, if real orbitals are considered.
A * orbital, pi antibonding orbital, will also produce a phase change when rotated
about the internuclear axis. The * orbital also has a second nodal plane between
the nuclei.[11][12][13][14]
symmetry[edit]