AnS2(2+)_cations

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.

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Please use this identifier to cite or link to this collection: doi:10.19061/iochem-bd-1-30

This dataset derived results are published in:

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

Journal: PCCP

DOI: 10.1039/c7cp01446e

PreviewTitleAuthor(s)ProgramCalculation typeMethod(s)Basis SetLinksEnergySolv.Vibr.Orb.
thumbnail.jpeg/ThS2(2+) ThS2(2+)_linearBandeira, NunoMolcas; v8.0.14-09-21Single pointHFANO-RCC-
thumbnail.jpeg/ThS2(2+) ThS2(2+)_triangularBandeira, NunoMolcas; v8.0.14-09-21Single pointHFANO-RCC-
thumbnail.jpeg/ThS2(2+) ThS2(2+)_singlet_optimisationBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/ThS2(2+) ThS2(2+)_triplet_optimisationBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/UO2(2+) Triplet_eta2-UO2(2+)_CAS(4,8)PT2Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/UO2(2+) Quintet_eta2-UO2(2+)_CAS(4,8)PT2Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/UO2(2+) Triplet_CAS(4,8)PT2_single_pointBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/US2(2+)/S=0 MP2_Optimisation,_linear_moleculeBandeira, NunoMolcas; v8.0.14-09-21Single pointHFANO-RCC-
thumbnail.jpeg/US2(2+)/S=0 CAS(4,8)PT2_single_point_linearBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/US2(2+)/S=0 CAS(4,8)PT2_opt_triangularBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/US2(2+)/S=1 CAS(4,8)PT2_optimisation_tripletBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/US2(2+)/S=1 Triplet_CAS(12,13)PT2Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/US2(2+)/S=2 CAS(4,8)PT2_quintet_optimisationBandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=3 Septet_triangularBandeira, NunoMolcas; v8.0.15-06-18Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=2 Triangular_S=2Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=2 Linear_S=2Bandeira, NunoMolcas; v8.0.15-06-18Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=1 Linear_S=1Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=1 Triangular_S=1Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=0 Linear_S=0Bandeira, NunoMolcas; v8.0.15-06-18Single pointCASSCF; CASPT2ANO-RCC-
thumbnail.jpeg/PuS2(2+)/S=0 triangular_S=0_Bandeira, NunoMolcas; v8.0.14-09-21Single pointCASSCF; CASPT2ANO-RCC-
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