Valence Bond Theory - VB Theory Today

VB Theory Today

Valence bond theory now complements molecular orbital (MO) theory, which does not adhere to the VB idea that electron pairs are localized between two specific atoms in a molecule but that they are distributed in sets of molecular orbitals which can extend over the entire molecule. MO theory can predict magnetic and ionization properties in a straightforward manner, while valence bond theory gives similar results but is more complicated. Valence bond theory views aromatic properties of molecules as due to resonance between Kekulé, Dewar and possibly ionic structures, while molecular orbital theory views it as delocalization of the π-electrons. The underlying mathematics are also more complicated, limiting VB treatment to relatively small molecules. On the other hand, VB theory provides a much more accurate picture of the reorganization of electronic charge that takes place when bonds are broken and formed during the course of a chemical reaction. In particular, valence bond theory correctly predicts the dissociation of homonuclear diatomic molecules into separate atoms, while simple molecular orbital theory predicts dissociation into a mixture of atoms and ions.

More recently, several groups have developed what is often called modern valence bond theory. This replaces the overlapping atomic orbitals by overlapping valence bond orbitals that are expanded over a large number of basis functions, either centered each on one atom to give a classical valence bond picture, or centered on all atoms in the molecule. The resulting energies are more competitive, with energies from calculations where electron correlation is introduced based on a Hartree–Fock reference wavefunction. The most recent text is by Shaik and Hiberty.