TY - JOUR
T1 - Spin-orbit CI study on multiplet terms of trivalent lanthanide cations
AU - Sanoyama, E.
AU - Kobayashi, H.
AU - Yabushita, S.
N1 - Funding Information:
The authors present this paper as a tribute to Professor Sigeru Huzinaga in commemoration of his 70th birthday. It is a real pleasure to acknowledge Professor Huzinaga's contributions to atomic and molecular electronic structure theory. The authors thank the computer center, Institute for Molecular Science, Okazaki, Japan, for the use of the SP2 and SX3 computers for this work. This work was supported in part by the Grants in Aid for Scientific Research from the Minister of Education, Culture, and Science of Japan.
PY - 1998/9/28
Y1 - 1998/9/28
N2 - 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.
AB - 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.
KW - Landé interval rule
KW - Lanthanide
KW - Relativistic effective core potential
KW - Spin-orbit CI
KW - Spin-orbit effect
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U2 - 10.1016/S0166-1280(98)00171-7
DO - 10.1016/S0166-1280(98)00171-7
M3 - Article
AN - SCOPUS:0001522818
SN - 2210-271X
VL - 451
SP - 189
EP - 204
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
IS - 1-2
ER -