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Concerted Hydrogen-Bond Dynamics in the Transport Mechanism of the Hydrated Proton: A First-Principles Molecular Dynamics Study

2009; American Physical Society; Volume: 103; Issue: 23 Linguagem: Inglês

10.1103/physrevlett.103.238302

1092-0145

Timothy C. Berkelbach, Hee‐Seung Lee, Mark E. Tuckerman,

Advanced Chemical Physics Studies

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.