title: Simple and surprisingly accurate approach to the chemical bond obtained from dimensional scaling.
abstract: We present a new dimensional scaling transformation of the Schrödinger equation for the two electron bond. This yields, for the first time, a good description of the bond via D scaling. There also emerges, in the large-D limit, an intuitively appealing semiclassical picture, akin to a molecular model proposed by Bohr in 1913. In this limit, the electrons are confined to specific orbits in the scaled space, yet the uncertainty principle is maintained. A first-order perturbation correction, proportional to 1/D, substantially improves the agreement with the exact ground state potential energy curve. The present treatment is very simple mathematically, yet provides a strikingly accurate description of the potential curves for the lowest singlet, triplet, and excited states of H2. We find the modified D-scaling method also gives good results for other molecules. It can be combined advantageously with Hartree-Fock and other conventional methods.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
authors.forename: Anatoly A
authors.initials: AA
authors.lastname: Svidzinsky
authors.forename: Marlan O
authors.initials: MO
authors.lastname: Scully
authors.forename: Dudley R
authors.initials: DR
authors.lastname: Herschbach