Relativistic coupled-cluster simulation of the kinetics of the hydrolysis of uranium hexafluoride

Abstract

Uranium hexafluoride ( UF 6 ) is used ubiquitously in the nuclear fuel cycle. Its spontaneous hydrolysis in the presence of atmospheric moisture is well known but the associated reaction mechanism is poorly understood. Here a computational study was undertaken with the aim of characterizing the rate-limiting step of the hydrolysis of UF 6 under dry conditions. Toward this end, we began by examining the convergence of various energy contributions to the atomization enthalpy ( Δ H at ) of UF 6 and its hydrolysis product, UO 2 F 2 . This enabled a refinement of our previous composite method, resulting in a composite method with improved accuracy that also scales well by leveraging existing massively-parallel codes. We find that extremely high levels of theory are required to obtain Δ H at within experimental error bars, in agreement with the literature. Having calibrated our composite scheme, we proceed to investigate approximations appropriate for computing accurate binding energies and barrier heights on the potential energy surface governing the hydrolysis of UF 6 . In combination with high-accuracy relative energies, a master equation approach is used to generate rate constants, and comparisons are made with recent measurements [Richards et al., RSC Adv., 2020, 10, 34729]. Based on kinetic and equilibrium arguments, we conclude that the hydrolysis of U F 6 , when proceeding under very dry conditions, is unlikely to be initiated via U F 6 + H 2 O → UF 5 OH + HF type reactions. Finally, computed equilibrium constants and rate coefficients are tabulated for the temperature range 300–1800 K.