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

被引：204

作者：

Berkelbach, Timothy C. ^{[1
]}

Lee, Hee-Seung ^{[2
]}

Tuckerman, Mark E. ^{[3
,4
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

[2] Univ N Carolina, Dept Chem & Biochem, Wilmington, NC 28403 USA

[3] NYU, Dept Chem, New York, NY 10003 USA

[4] NYU, Courant Inst Math Sci, New York, NY 10003 USA

来源：

PHYSICAL REVIEW LETTERS | 2009年 / 103卷 / 23期

关键词：

DENSITY-FUNCTIONAL THEORY; AB-INITIO; LIQUID WATER; SIMULATIONS; SOLVATION; REORIENTATION; GROTTHUSS; IONS;

D O I：

10.1103/PhysRevLett.103.238302

中图分类号：

O4 [物理学];

学科分类号：

0702 ;

摘要：

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.

引用

页数：4

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