TY - JOUR
T1 - Synthesis, structure and bonding of actinide disulphide dications in the gas phase
AU - Lucena, Ana F.
AU - Bandeira, Nuno A. G.
AU - Pereira, Cláudia C. L.
AU - Gibson, John K.
AU - Marçalo, Joaquim
PY - 2017
Y1 - 2017
N2 - Actinide disulphide dications, AnS22+, were produced in the gas phase for An = Th and Np by reaction of An2+ 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 ThIVS22+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a AnIIIS22+ species. 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.
AB - Actinide disulphide dications, AnS22+, were produced in the gas phase for An = Th and Np by reaction of An2+ 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 ThIVS22+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a AnIIIS22+ species. 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.
KW - uranyl
KW - ions
KW - atoms
KW - analogs
KW - quantum-chemical calculations
KW - molecular wave-functions
KW - quasi-relativistic dft
KW - ano basis-sets
KW - infrared-spectra
KW - chemistry
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85019998665&origin=resultslist&sort=plf-f&src=s&st1
U2 - 10.1039/C7CP01446E
DO - 10.1039/C7CP01446E
M3 - Article
SN - 1463-9076
SP - 10685
EP - 10694
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
ER -