Reactions of Atomic Thorium and Uranium Cations with SF₆ Studied by Guided Ion Beam Tandem Mass Spectrometry

The fundamental chemistry of the thorium and uranium fluorides continues to be an area of interest because of the use of thorium and uranium fluoride compounds in nuclear fuel systems. Here, we study the reaction of thorium cations with sulfur hexafluoride for the first time and revisit the reaction of uranium cations with sulfur hexafluoride. By using guided ion beam tandem mass spectrometry, we explore the reaction pathways that become accessible well above thermal energies (E ∼ 0.04 eV). Overall, we find that both Th⁺ and U⁺ react very efficiently with SF₆, approaching the collision limit at both thermal and elevated energies. The primary products observed at low energies include Th_1-3⁺, UF_1-4⁺, and SF_1-4⁺, all of which are formed in barrierless, exothermic processes. SF₅⁺ was also observed, although the pressure dependence of this channel reveals that SF₅⁺ forms exothermically through secondary reactions, which the energy dependences suggest result from reactions between ThF₂⁺ and UF₃⁺ with SF₆. At higher energies, both AnF₃⁺ products are observed to decay to AnF⁺ + F₂, and both SF₄⁺ and SF₂⁺ exhibit cross sections with endothermic features. For both systems, the rise in SF₄⁺ can be attributed to a secondary collision between AnF⁺ with SF₆ on the basis of the pressure dependence of the SF₄⁺ channel at higher energies, and the rise in SF₂⁺ appears to result from the decomposition of SF₃⁺ to SF₂⁺ + F.