Relativistic correlating basis sets for actinide atoms from 90Th to 103Lr

✍ Scribed by Takeshi Noro; Masahiro Sekiya; You Osanai; Toshikatsu Koga; Hisashi Matsuyama

• Book ID: 102305981
• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 104 KB
• Volume: 28
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20537

✦ Synopsis

Abstract

For 14 actinide atoms from ~90~Th to ~103~Lr, contracted Gaussian‐type function sets are developed for the description of correlations of the 5__f__, 6__d__, and 7__s__ electrons. Basis sets for the 6__d__ orbitals are also prepared, since the orbitals are important in molecular environments despite their vacancy in the ground state of some actinides. A segmented contraction scheme is employed for the compactness and efficiency. Contraction coefficients and exponents are so determined as to minimize the deviation from accurate natural orbitals of the lowest term arising from the 5__f__^n−1^6__d__^1^7__s__^2^ configuration. The spin‐free relativistic effects are considered through the third‐order Douglas‐Kroll approximation. To test the present correlating sets, all‐electron calculations are performed on the ground state of ~90~ThO molecule. The calculated spectroscopic constants are in excellent agreement with experimental values. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007