title: Water O-H bond activation by gas-phase plutonium atoms: reaction mechanisms and ab initio molecular dynamics study.
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.
authors.affiliation: Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, 610065 (China).
authors.forename: Peng
authors.initials: P
authors.lastname: Li
authors.forename: Wenxia
authors.initials: W
authors.lastname: Niu
authors.forename: Tao
authors.initials: T
authors.lastname: Gao
authors.forename: Hongyan
authors.initials: H
authors.lastname: Wang
keywords: gas phase; hydrolysis; molecular dynamics; plutonium; reaction mechanisms