Natural Bond Orbital Study on the Nature of Binding in the H2 Molecule

Abstract We use the natural bond orbital (NBO) method to decompose a MO wavefunction into the intuitive valence bond (VB) structures. At least two natural orbital type MO are required to describe the essential binding of the H2 molecule at all inter nuclear distances. At first the MO wavefunction is transformed into an unrestricted Hartree‐Fock wave‐function consisted of non‐orthogonal localized orbitals u' and v', and then the NBO method is used to decompose u' and v' into the physical meaningful orthogonal localized orbitals. Our results show that the orbitals u' and v' are decomposed into an atomic and an overlap parts. The latter part gives rise to the conventional ionic structure in the VB picture.