Spin-orbit CI study on multiplet terms of trivalent lanthanide cations

E. Sanoyama, H. Kobayashi, S. Yabushita

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

In this paper we calculate the low energy spin-orbit multiplet terms of trivalent lanthanide cations Ce3+ to Yb3+, except for Gd3+, with three different RECPs, including the spin-orbit effect explicitly, to assess their reliability. Although there is fairly good agreement with experiment for the ground LS multiplet splittings, implying the accuracy of the spin-orbit Hamiltonian, the agreement is less for the higher LS terms. The source of the error was found to be the significant semi-core correlations in the 4d, 5s, and 5p shells, which have very strong effects on the spin-free excitation energies. The degree of the intermediate coupling is also studied and related to the deviation from the Landé interval rule. The differences between the intermediate coupling method and the fully variational spin-orbit CI method are numerically analyzed.

Original languageEnglish
Pages (from-to)189-204
Number of pages16
JournalJournal of Molecular Structure: THEOCHEM
Volume451
Issue number1-2
DOIs
Publication statusPublished - 1998 Sep 28

Keywords

  • Landé interval rule
  • Lanthanide
  • Relativistic effective core potential
  • Spin-orbit CI
  • Spin-orbit effect

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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