Spin-orbit configuration interaction study of the electronic structure of the 5f(2) manifold of U4+ and the 5f manifold of U5+
2008 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 128, no 15, 154310- p.Article in journal (Refereed) Published
The energy levels of the 5f configuration of U5+ and 5f(2) configuration of U4+ have been calculated in a dressed effective Hamiltonian relativistic spin-orbit configuration interaction framework. Electron correlation is treated in the scalar relativistic scheme with either the multistate multireference second-order multiconfigurational perturbation theory (MS-CASPT2) or with the multireference single and double configuration interaction (MRCI) and its size-extensive Davidson corrected variant. The CASPT2 method yields relative energies which are lower than those obtained with the MRCI method, the differences being the largest for the highest state S-1(0) of the 5f(2) manifold. Both valence correlation effects and spin-orbit polarization of the outer-core orbitals are shown to be important. The satisfactory agreement of the results with experiments and four-component correlated calculations illustrates the relevance of dressed spin-orbit configuration interaction methods for spectroscopy studies of heavy elements. (c) 2008 American Institute of Physics.
Place, publisher, year, edition, pages
2008. Vol. 128, no 15, 154310- p.
2nd-order perturbation-theory, blue up-conversion, parametric analysis, solvation models, single-crystals, actinide ions, ci method, basis-set, spectrum, luminescence
IdentifiersURN: urn:nbn:se:su:diva-58553DOI: 10.1063/1.2888560ISI: 000255228900031OAI: oai:DiVA.org:su-58553DiVA: diva2:421096
authorCount :42011-06-072011-06-032011-06-07Bibliographically approved