Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study

Abstract

The energetics of hydrolysis reactions for high oxidation states oxo/hydroxo monomeric actinide species (

A theoretical investigation of the hydrolysis of uranium hexafluoride: the initiation mechanism and vibrational spectroscopy

“…This underscores the difficulty of accurately generating actinide energy differences. 101,102 Evaluation of the relative performance of various DFT methods was carried out next, with the results compiled in Table 4. Comparing various DFT approaches to reference CC values produced a set of MDs, MSEs, and MUEs.…”

Matrix-Isolation Infrared Spectra and Electronic Structure Calculations for Dinitrogen Complexes with Uranium Trioxide Molecules UO3(η1-NN)1–4

“…Hunt et al reported a UO 3 –O 2 complex at 842.4 cm –1 in solid argon where O 2 perturbs the strongest UO 3 ν 4 absorption at 852.5 cm –1 . , However, the properties of bonding between UO 3 and O 2 have not been addressed clearly. Several calculations have been carried out on the reactions of the UO 3 molecule with H 2 O and UF 6 . , Unfortunately, the computed results lack experimental support. Accordingly, research on the interaction of UO 3 with other species is expected to provide a new perspective on its reaction and bonding behaviors.…”

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

“…Many experimental and theoretical researchers have devoted effort to studying the structures, bonding and reactivity of thorium oxide clusters. [7,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Among them, several studies have revealed the stable structures of thorium oxide clusters. [21][22][23][31][32][33]35] Anionic photoelectron spectra combined with theoretical calculations have been carried out to explore the electronic structures and chemical bonding of the gasphase ThO n À /0 (n = 1-3) clusters.…”

“…Dixon et al also theoretically studied the reaction mechanism of ThO 2 with H 2 O, and ThO(OH) 2 and Th(OH) 4 were proposed as the hydrolysis products. [24][25][26][27] Although the experimental and theoretical studies of ThO 2 reacting with H 2 O have been reported in the previous studies, the comparison studies on the hydrolysis mechanisms of thorium oxides with the other oxygen contents are still lacked. Additionally, an interesting work on the hydrolysis of the actinide oxides (An=Th, Pa, U, Np, Pu) was recently reported by Dixon and co-workers.…”

“…Additionally, an interesting work on the hydrolysis of the actinide oxides (An=Th, Pa, U, Np, Pu) was recently reported by Dixon and co-workers. [26] They found the + 6 oxidation state of actinide was the turning point in determining the formation of hydrolysis products, i. e., the forming of hydroxide was favoured for actinide metal below this oxidation state, conversely the hydration compound. Adjusting the oxygen content of oxides often bring about the oxygen-deficient site and the other reactive oxygen species, together with changing their chemical behaviour.…”