Thermochemistry of uranium sulfide cations: guided ion beam and theoretical studies of reactions of U⁺ and US⁺ with CS₂ and collision-induced dissociation of US⁺

Abstract

Reactions of atomic uranium cations with carbon disulfide form US⁺ in an efficient exothermic reaction and UCS⁺ in an inefficient endothermic process. The subsequent reaction of US⁺ with CS₂ forms US₂⁺ in an endothermic process having a low energy threshold. At much higher energies, UCS₂⁺ and UCS⁺ are also formed. Collision-induced dissociation of US⁺ with Xe yields U⁺ + S exclusively in an endothermic reaction. Analysis of the kinetic energy dependent cross sections of the endothermic processes yields the 0 K bond dissociation energies of 5.73 ± 0.15 eV for U⁺ – S, 3.89 ± 0.08 eV for SU⁺ – S, 1.69 ± 0.17 eV for U⁺ – CS, 2.78 ± 0.33 eV for U⁺ – CS₂, 1.53 ± 0.30 eV for SU⁺ – CS, and 5.65 ± 0.39 eV for S – UCS⁺. Theory is used to explore the structures and electron configurations of US⁺, US₂⁺, UCS⁺, and UCS₂⁺. The thermochemistry measured in this study is further compared to analogous values previously determined for select group 3 metals, lanthanides, and actinides.

GRAPHICAL ABSTRACT

KEYWORDS:

• Actinide
• bond dissociation energy
• chalcogenide

Acknowledgements

This grants of computational time from the Centre for High Performance Computing (CHPC) at the University of Utah.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work was supported by Heavy Element Chemistry Program, Office of Basic Energy Sciences, U. S. Department of Energy: [grant no DE-SC0012249].