title: Concerted hydrogen-bond dynamics in the transport mechanism of the hydrated proton: a first-principles molecular dynamics study.
abstract: First-principles molecular dynamics calculations performed in a fully converged basis set are used to reveal new details about the mechanism of the anomalous proton-transport process in water, a fundamental question dating back over 200 years. By separating actual structural diffusion from simple rattling events, wherein a proton shuttles forth and back in a hydrogen bond, it is found that the former are driven by a concerted mechanism in which hydronium begins to accept a hydrogen bond from a donor water molecule while the proton-receiving water molecule simultaneously loses one of its acceptor hydrogen bonds. The kinetics of the process are found to be in good agreement with recent experiments.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Berkelbach
authors.forename: Hee-Seung
authors.initials: HS
authors.lastname: Lee
authors.forename: Mark E
authors.initials: ME
authors.lastname: Tuckerman
mesh_terms: D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D009038:Motion; D009861:Onium Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D014867:Water / Q000737:chemistry*
chemical_list: D009861:Onium Compounds; D011522:Protons; D014867:Water; C027727:hydronium ion; D010100:Oxygen