Relativistic correlating basis sets for lanthanide atoms from Ce to Lu

✍ Scribed by Masahiro Sekiya; Takeshi Noro; Eisaku Miyoshi; You Osanai; Toshikatsu Koga

• Book ID: 102305743
• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 105 KB
• Volume: 27
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20357

✦ Synopsis

Abstract

Contracted Gaussian‐type function (CGTF) sets for the description of the 4__f__ subshell correlation and of the 6__s__ and 5__d__ subshell correlation are developed for lanthanide atoms from Ce to Yb. Also prepared are basis sets for the 5__d__ orbitals, which are vacant in the ground states of most lanthanide atoms but are essential in molecular environments. In addition, correlating CGTF sets for the 4__f__ subshell correlation are supplemented for the Lu atom. A segmented contraction scheme is employed for their compactness and efficiency. Contraction coefficients and exponents are determined by minimizing the deviation from accurate natural orbitals generated from configuration interaction calculations that include relativistic effects through the third‐order Douglas–Kroll approximation. All‐electron and model core potential calculations with the present correlating sets are performed on the ground state of the diatomic CeO molecule. The calculated spectroscopic constants are in good agreement with experimental values. © 2006 Wiley Periodicals, Inc. J Comput Chem 27:463–470, 2006