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

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

Content Provider	United States Department of Energy Office of Scientific and Technical Information (OSTI.GOV)
Author	Lucena, Ana F. Bandeira, Nuno A. G. Pereira, Claudia C. L. Gibson, John K. Marcalo, Joaquim
Organization	Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Abstract	Actinide disulphide dications, AnS₂²⁺, 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, An²⁺ 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 AnS₂²⁺ 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 US₂²⁺. The CASPT2 results showed that, like in the case of uranium, the new AnS₂²⁺ 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 S₂²⁺ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a An^IIIS₂²⁺ species. Finally, the computations also revealed 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.
Sponsorship	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)
Related Links	https://www.osti.gov/biblio/1435072
Starting Page	10685
Ending Page	10694
Page Count	10
File Format	PDF
ISSN	14639076
DOI	10.1039/c7cp01446e
Journal	Physical Chemistry Chemical Physics. PCCP
Volume Number	19
Issue Number	16
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2017-01-01
Publisher Place	United States
Access Restriction	Open
Subject Keyword	INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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