Polarized basis sets of Slater-type orbitals: H to Ne atoms

✍ Scribed by I. Ema; J. M. García de la Vega; G. Ramírez; R. López; J. Fernández Rico; H. Meissner; J. Paldus

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 95 KB
• Volume: 24
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.10227

✦ Synopsis

Abstract

We present three Slater‐type atomic orbital (STO) valence basis (VB) sets for the first and second row atoms, referred to as the VB1, VB2, and VB3 bases. The smallest VB1 basis has the following structure: [3, 1] for the H and He atoms, [5, 1] for Li and Be, and [5, 3, 1] for the B to Ne series. For the VB2 and VB3 bases, both the number of shells and the number of functions per shell are successively increased by one with respect to VB1. With the exception of the H and Li atoms, the exponents for the VB1 bases were obtained by minimizing the sum of the Hartree–Fock (HF) and frozen‐core singles and doubles configuration interaction (CISD FC) energies of the respective atoms in their ground state. For H and Li, we minimized the sum of the HF and CISD FC energies of the corresponding diatoms (i.e., of H~2~ or Li~2~) plus the ground‐state energy of the atom. In the case of the VB2 basis sets, the sum that was minimized also included the energies of the positive and negative ions, and for the VB3 bases, the energies of a few lowest lying excited states of the atom. To account for the core correlations, the VB__x__ (x = 1, 2, and 3) basis sets for the Li to Ne series were enlarged by one function per shell. The exponents of these extended (core‐valence, CV) basis sets, referred to, respectively, as the CVB__x__ (x = 1, 2, and 3) bases, were optimized by relying on the same criteria as in the case of the VB__x__ (x = 1, 2, and 3) bases, except that the full CISD rather than CISD FC energies were employed. We show that these polarized STO basis sets provide good HF and CI energies for the ground and excited states of the atoms considered, as well as for the corresponding ions. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 859–868, 2003