Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals

来自万方

喜欢 0

阅读量：

912

作者：

PJ Hay，WR Wadt

展开

摘要：

Ab initioeffective core potentials (ECP's) have been generated to replace the innermost core electron for third‐row (K–Au), fourth‐row (Rb–Ag), and fifth‐row (Cs–Au) atoms. The outermost core orbitals—corresponding to thens2np6configuration for the three rows here—are not replaced by the ECP but are treated on an equal footing with thend, (n+1)sand (n+1)pvalence orbitals. These ECP's have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP. The ECP's for the forth and fifth rows also incorporate the mass–velocity and Darwin relativistic effects into the potentials. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3s,3p,3d,4s,4p), (4s,4p,4d,5s,5p), and (5s,5p,5d,6s,6p) ortibals of the three respective rows.

展开

关键词：

Theoretical or Mathematical/ ab initio calculations atomic structure/ ab initio effective core potentials mass velocity effects analytic fits molecular calculations K Au outermost core orbitals innermost core electron ns2np6 configuration valence orbitals Darwin relativistic effects multicenter integral evaluation Gaussian orbital valence basis sets/ A3120 Specific calculations and results for atoms and molecules