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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
Authors:
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
Type:
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
Publisher:
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
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1435072

Lucena, Ana F., Bandeira, Nuno A. G., Pereira, Claudia C. L., Gibson, John K., and Marcalo, Joaquim. Synthesis, structure and bonding of actinide disulphide dications in the gas phase. United States: N. p., Web. doi:10.1039/c7cp01446e.
Lucena, Ana F., Bandeira, Nuno A. G., Pereira, Claudia C. L., Gibson, John K., & Marcalo, Joaquim. Synthesis, structure and bonding of actinide disulphide dications in the gas phase. United States. doi:10.1039/c7cp01446e.
Lucena, Ana F., Bandeira, Nuno A. G., Pereira, Claudia C. L., Gibson, John K., and Marcalo, Joaquim. 2017. "Synthesis, structure and bonding of actinide disulphide dications in the gas phase". United States. doi:10.1039/c7cp01446e. https://www.osti.gov/servlets/purl/1435072.
@article{osti_1435072,
title = {Synthesis, structure and bonding of actinide disulphide dications in the gas phase},
author = {Lucena, Ana F. and Bandeira, Nuno A. G. and Pereira, Claudia C. L. and Gibson, John K. and Marcalo, Joaquim},
abstractNote = {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 ThIV S22+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a AnIIIS22+ 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.},
doi = {10.1039/c7cp01446e},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 16,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}