Best optimized One-Electron Wave-Functions;
I. The General Procedure of Optimization;
II. Isoelectronic Series of Li, Be, B, and C;
III. Direct Examination of Optimization Effectiveness;
IV. Ionization Energies of Atoms.
International Journal of Quantum Chemistry, Vol. X, 719-746 (1976).
(only the abstract of the 1st part of the series is given here for shortness)
A new effective semiempirical method of optimization of one-electron wave-functions has been proposed without a necessity to determine any exact many-electron wave-function. The method designed for LCAO MO calculations is based on a concept of interacting quasi-particles and on nonorthogonal spin-orbitals. “Mixing” of the pure single-particle wave-functions is optimized by means of the procedure which requires only one empirical parameter for each considered state of the whole system. The procedure results in optimal distribution of total electron charge between the individual spin-orbitals. The general method has been illustrated with calculations for the ground state of lithium atom.