Synthesis, structure and bonding of actinide disulphide dications in the gas phase [electronic resource].
- Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2017.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- pages 10,685-10,694 : digital, PDF file
- Additional Creators:
- Lawrence Berkeley National Laboratory
United States. Department of Energy. Office of Basic Energy Sciences
United States. Department of Energy. Office of Scientific and Technical Information
- Actinide disulphide dications, AnS<sub>2</sub><sup>2+</sup>, 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<sup>2+</sup> 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<sub>2</sub><sup>2+</sup> 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<sub>2</sub><sup>2+</sup>. The CASPT2 results showed that, like in the case of uranium, the new AnS<sub>2</sub><sup>2+</sup> 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<sup>IV</sup> S<sub>2</sub><sup>2+</sup> species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a An<sup>III</sup>S<sub>2</sub><sup>2+</sup> 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.
- Published through SciTech Connect.
Physical Chemistry Chemical Physics. PCCP (Print) 19 16 ISSN 1463-9076; PPCPFQ AM
Ana F. Lucena; Nuno A. G. Bandeira; Claudia C. L. Pereira; John K. Gibson; Joaquim Marcalo.
Foundation for Science and Technology (FCT) Portugal
Spanish Ministerio de Economia y Competitividad (MINECO)
- Funding Information:
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