Exploring Unorthodox Dimensions for Two-Electron Atoms.

Melding quantum and classical mechanics is an abiding quest of physical chemists who strive for heuristic insights and useful tools. We present a surprisingly simple and accurate treatment of ground-state two-electron atoms. It makes use of only the dimensional dependence of a hydrogen atom, together with the exactly known first-order perturbation value of the electron-electron interaction, both quintessentially quantum, and the D → ∞ limit, entirely classical. The result is an analytic formula for D-dimensional two-electron atoms with Z ≥ 2. For D = 3 helium, it gives accuracy better than 2 millihartrees, which is better than current density functional theory. A kindred explicit formula for correlation energy exploits interpolation between D → ∞ and D = 1 or 2; when added to the Hartree-Fock energy, it improves accuracy for D = 3 helium to better than 0.1 millihartrees.