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Title: Synthesis, structure and bonding of actinide disulphide dications in the gas phase

Actinide disulphide dications, AnS 2 2+, were produced in the gas phase for An = Th and Np by reaction of An 2+ cations with the sulfur-atom donor COS, in a sequential abstraction process of two sulfur atoms, as examined by FTICR mass spectrometry. For An = Pu and Am, An 2+ ions were unreactive with COS and did not yield any sulphide species. High level multiconfigurational (CASPT2) calculations were performed to assess the structures and bonding of the new AnS 2 2+ species obtained for An = Th, Np, as well as for An = Pu to examine trends along the An series, and for An = U to compare with a previous experimental study and DFT computational scrutiny of US 2 2+. The CASPT2 results showed that, like in the case of uranium, the new AnS 2 2+ ions have ground states with triangular geometries, corresponding to the presence of a persulphide in the case of thorium that formally leads to a stable Th IV S 2 2+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a An IIIS 2 2+ species. Finally, the computations also revealedmore » that linear thioactinyl structures are higher in energy, with a difference that increases fourfold upon moving from U to Pu, apparently indicating that it will be even more pronounced for Am.« less
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1]
  1. Univ. de Lisboa (Portugal). Centro de Ciencias e Tecnologias Nucleares, Inst. Superior Tecnico
  2. The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. de Lisboa (Portugal). Centro de Quimica Estrutural, Instituto Superior Tecnico, Inst. Superior Tecnico
Publication Date:
Grant/Contract Number:
AC02-05CH11231; SFRH/BD/70475/2010; SFRH/BPD/110419/2015; PTDC/QEQ-QIN/3414/2014; CTQ2014-52824-R
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 16; Journal ID: ISSN 1463-9076
Royal Society of Chemistry
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Foundation for Science and Technology (FCT) Portugal; Spanish Ministerio de Economia y Competitividad (MINECO)
Country of Publication:
United States
OSTI Identifier: