Hydrogenic orbitals as minimum-basis functions for SCF calculations

✍ Scribed by Donald W. Boerth; F. A. Van-Catledge

• Book ID: 104580048
• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 845 KB
• Volume: 18
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560180406

✦ Synopsis

Abstract

The orbital approximation that polyelectronic atoms can be qualitatively described by using hydrogenlike orbitals was tested quantitatively. Hydrogenic atomic orbitals (HTO's) were investigated as best‐atom minimum‐basis set functions and were compared to best‐atom Slater orbitals (STO's). The two sets of wave functions were compared in terms of the ground‐state energies, the electron densities at the nuclei, charge distribution in space, electron populations, and atomic “radii.” In the atomic calculations the HTO's give somewhat poorer atom descriptions that STO's. SCF calculations on diatomic molecules (N~2~, CO, and HF) indicate that while HTO's give higher molecular energies, they closely mimic STO's in terms of electronic reorganization. The principal difference between HTO and STO results was attributed to the compact nature of the HTO 2__s__ orbital.