Hyperbolic cosine functions applied to atomic calculations: singly-charged cations and anions

• Published in: Chemical physics letters Vol. 304; no. 5; pp. 445 - 449
• Main Authors: Koga, Toshikatsu, Kuroki, Youichi, Tada, Shiho
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 07.05.1999
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/S0009-2614(99)00335-8

The radial basis functions r n−1 exp(− αr)cosh( βr+ γ), proposed recently for Roothaan–Hartree–Fock calculations of neutral atoms, are applied to the 53 singly-charged cations Li + through Cs + and 43 anions H − through I − (excluding 10 unstable anions) within the minimal-basis framework. Our systematic study of the 96 ions in their ground states confirms that the basis functions are useful for a compact analytical approximation of Hartree–Fock wavefunctions of ionic species as well. Compared to the values of the conventional Slater-type functions, the total energies are lower by 12.6 hartree for Cs + and by 12.1 for I −. Orbital energies are also improved; the errors relative to the Hartree–Fock limit values never exceed 0.024 hartree.