Roles of H-Bonding and Hydride Solvation in the Reaction of Hydrated (Di)electrons with Water to Create H 2 and OH

• Published in: Journal of chemical theory and computation
• Main Authors: Borrelli, William R, Guardado Sandoval, José L, Mei, Kenneth J, Schwartz, Benjamin J
• Format: Journal Article
• Language: English
• Published: United States 07.08.2024
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.4c00780

Even though single hydrated electrons ( 's) are stable in liquid water, two hydrated electrons can bimolecularly react with water to create H and hydroxide: + + 2H O → H + 2OH . The rate of this reaction has an unusual temperature and isotope dependence as well as no dependence on ionic strength, which suggests that cosolvation of two electrons as a single hydrated dielectron ( ) might be an important intermediate in the mechanism of this reaction. Here, we present an ab initio density functional theory study of this reaction to better understand the potential properties, reactivity, and experimental accessibility of hydrated dielectrons. Our simulations create hydrated dielectrons by first simulating single 's and then injecting a second electron, providing a well-defined time zero for formation and offering insight into a potential experimental route to creating dielectrons and optically inducing the reaction. We find that immediately forms in every member of our ensemble of trajectories, allowing us to study the molecular mechanism of H and OH formation. The subsequent reaction involves separate proton transfer steps with a generally well-defined hydride subintermediate. The time scales for both proton transfer steps are quite broad, with the first proton transfer step spanning times over a few ps, while the second proton transfer step varies over ∼150 fs. We find that the first proton transfer rate is dictated by whether or not the reacting water is part of an H-bond chain that allows the newly created OH to rapidly move by Grotthuss-type proton hopping to minimize electrostatic repulsion with H . The second proton transfer step depends significantly on the degree of solvation of H , leading to a wide range of reactive geometries where the two waters involved can lie either across the dielectron cavity or more adjacent to each other. This also allows the two proton transfer events to take place either effectively concertedly or sequentially, explaining differing views that have been presented in the literature.