title: Relativistic correlating basis sets for lanthanide atoms from Ce to Lu.
abstract: Contracted Gaussian-type function (CGTF) sets for the description of the 4f subshell correlation and of the 6s and 5d subshell correlation are developed for lanthanide atoms from Ce to Yb. Also prepared are basis sets for the 5d 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 4f 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.
authors.affiliation: Department of Intercultural Studies, Tomakomai Komazawa University, Tomakomai, Hokkaido 059-1292, Japan. msekiya@be.to
authors.forename: Masahiro
authors.initials: M
authors.lastname: Sekiya
authors.forename: Takeshi
authors.initials: T
authors.lastname: Noro
authors.forename: Eisaku
authors.initials: E
authors.lastname: Miyoshi
authors.forename: You
authors.initials: Y
authors.lastname: Osanai
authors.forename: Toshikatsu
authors.initials: T
authors.lastname: Koga
mesh_terms: D000465:Algorithms; D002563:Cerium / Q000737:chemistry; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003198:Computer Simulation; D004583:Electrons; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008187:Lutetium / Q000737:chemistry; D008958:Models, Molecular; D008962:Models, Theoretical; D009686:Nuclear Physics; D011789:Quantum Theory
chemical_list: D028581:Lanthanoid Series Elements; D002563:Cerium; D008187:Lutetium; C030583:ceric oxide