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

E. Sanoyama, H. Kobayashi, Satoshi Yabushita

Research output: Contribution to journalArticle

18 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
Publication statusPublished - 1998 Sep 28

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Lanthanoid Series Elements
Orbit
Rare earth elements
Cations
Orbits
Positive ions
fine structure
orbits
cations
Hamiltonians
Excitation energy
Research Design
intervals
deviation
energy
Experiments
excitation

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Spin-orbit CI study on multiplet terms of trivalent lanthanide cations. / Sanoyama, E.; Kobayashi, H.; Yabushita, Satoshi.

In: Journal of Molecular Structure: THEOCHEM, Vol. 451, No. 1-2, 28.09.1998, p. 189-204.

Research output: Contribution to journalArticle

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