Change search
ReferencesLink to record
Permanent link

Direct link
Effects of the first hydration sphere and the bulk solvent on the spectra of the f(2) isoelectronic actinide compounds: U4+, NpO2+, and PuO22+
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
2010 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 12, no 5, 1116-1130 p.Article in journal (Refereed) Published
Abstract [en]

The electronic spectra of the 5f(2) isoelectronic actinide compounds U4+, NpO2+, and PuO22+ have been investigated theoretically both in gas phase and in solution. In the latter case the solvent was modelled by a saturated first hydration sphere, five water molecules for NpO2+, and PuO22+ and eight for U4+, and a continuum model describing the remaining solvent. The transition energies and oscillator strengths were obtained at the spin-orbit level using the relativistic wave function based multi-configuration methods CASPT2 (complete active space with second-order perturbation theory) and MRCI + DC (Davidson corrected multi-reference configuration interaction), followed by a spin-orbit CI based on a dressed effective spin-orbit Hamiltonian. This study is an attempt to contribute to an enhanced understanding of the electronic structure of tetravalent actinide ions and actinyl(V) and (VI) ions. The spin-orbit MRCI and spin-orbit CASPT2 transitions energies have been compared for the bare ions, leading us to the conclusion that the spin-orbit CASPT2 approach is reasonably accurate and can be used with confidence for the calculation of the hydrated species. The first hydration sphere and the bulk solvent lift degeneracies, but the effect on the transition energies is fairly small for the two actinyl ions, while it is larger, up to several thousands of wave numbers for U4+. The calculations allowed us to make assignments of the experimentally observed absorption spectra for all species. The computed transition energies and intensities compared favourably with experiment.

Place, publisher, year, edition, pages
2010. Vol. 12, no 5, 1116-1130 p.
Keyword [en]
National Category
Physical Sciences
Research subject
URN: urn:nbn:se:su:diva-50069DOI: 10.1039/b914222cISI: 000273863300011OAI: diva2:382737
authorCount :4Available from: 2011-01-03 Created: 2010-12-21 Last updated: 2011-01-03Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Wahlgren, Ulf
By organisation
Department of Physics
In the same journal
Physical Chemistry, Chemical Physics - PCCP
Physical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 17 hits
ReferencesLink to record
Permanent link

Direct link