Gas‐phase water activation by Th atom: Reaction mechanisms and topological analysis

Abstract

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.

Water OH Bond Activation by Gas‐Phase Plutonium Atoms: Reaction Mechanisms and Ab Initio Molecular Dynamics Study

“…The analyses of our calculations indicated that Pu + H 2 O and Th + H 2 O have similar mechanisms, [51] which are also similar to the insertion mechanism for the actinide cations. [6,14] However, despite this qualitative similarity, the Pu + H 2 O reaction had its own characteristics.…”

Theoretical study on the atmospheric reaction of CH3SH with O2

“…A large ELF value at a point (the redder area) is considered where electrons are greatly localized around it, suggesting that there may be covalent bond, lone pair, or atomic inner shell . Aside from ELF, the AIM analysis of the bond critical points (BCPs) method also has proven to be a very useful tool for studying chemical bonds . The presence of a BCP, the electron density ( ρ ) as well as its Laplacian (△ 2 ρ ) at BCP are the topological properties of a bond.…”

“…[57] Aside from ELF, the AIM analysis of the bond critical points (BCPs) method also has proven to be a very useful tool for studying chemical bonds. [58][59][60] The presence of a BCP, the electron density (ρ) as well as its Laplacian (5 2 ρ) at BCP are the topological properties of a bond. Negative and positive values of 5 2 ρ(BCP) indicate that electron density is locally concentrated and depleted, respectively.…”

Insight into the reaction mechanism of CH2SH with HO2: A density functional theory study

“…Generally, LOL has the same value range with ELF [0, 1]. Aside from LOL, AIM analysis by the bond critical points (BCPs) method was performed for describing the chemical bonds . The topological properties of a bond mainly consists of the BCP, corresponding electron density ( ρ [BCP]) and its Laplacian ∇ 2 ρ (BCP).…”

“…Aside from LOL, AIM analysis by the bond critical points (BCPs) method was performed for describing the chemical bonds. [49,50] The topological properties of a bond mainly consists of the BCP, corresponding electron density (ρ[BCP]) and its Laplacian r 2 ρ(BCP). Positive and negative values of r 2 ρ(BCP) denote that electron density is sparse and dense, respectively.…”