No abstract

A thorough description of the reaction mechanisms, taking into account different possible spin states, offers insights into the gas-phase reaction of plutonium atoms with water. Two possible reactions (isomerization and dehydrogenation) are presented. These reactions are found to be exothermic, with the best thermochemical conditions observed for the dehydrogenation reaction at around 23.5 kcal mol(-1). The nature of the chemical-bonding evolution along the reaction pathways are investigated by employing various methods including electron localization function, atoms in molecules, and Mayer bond order. Total, partial, and overlap population density of state diagrams and analyses are also presented. Reaction rates at elevated temperatures (T=298-2 000 K) are calculated by using variational transition-state theory with one-dimensional tunneling effects. In dynamics simulations, only the dehydrogenation reaction is observed, and found to be in good agreement with experimental values.

The gas-phase reactions of Th, Th 1 , and Th 21 with NH 3 were systematically investigated using different approaches of density functional theory. A detailed description of the reaction mechanisms along with the bonding character analysis offers deep insights into the reaction of Th species. Different possible spin multiplicities were considered as well as the effect of spin-orbit interactions.

Density functional theory calculations were performed to investigate the gas-phase reaction of Th atom with water. Three reaction pathways were identified, which leads to the formation of ThOH 1 H, ThO 1 H 2 , and H 2 ThO. The latter two are generated via the intermediate HThOH, and the H 2 ThO specie is generated from the isomerization of the HThOH intermediate. A thorough description of the reaction mechanism taking into account different possible spin states together with analysis of the electronic factors offer insights into the reactivity of the actinides atom. The obtained results are compared with the available experimental data. The three reaction pathways were found to be exothermic, in which the isomerization channel was observed with best thermochemical conditions around 123.9 kcal/mol. The nature of the chemical bonding evolution along the reaction pathways was studied using topological analysis including electron localization function, atoms-in-molecules, and natural bond orbital.

In this study, the equilibrium, electronic structures, bonding and topological properties of PuO2(H2O)n2+ (n = 1–6) complexes were systematically investigated.