Deprotonation of solvated formic acid: Car-Parrinello and metadynamics simulations

被引：52

作者：

Lee, JG

Asciutto, E

Babin, V

Sagui, C

Darden, T

Roland, C ^{[1
]}

机构：

[1] N Carolina State Univ, CHiPS, Raleigh, NC 27695 USA

[2] N Carolina State Univ, Dept Phys, Raleigh, NC 27695 USA

[3] NIEHS, Struct Biol Lab, Res Triangle Pk, NC 27709 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2006年 / 110卷 / 05期

关键词：

D O I：

10.1021/jp055809i

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The deprotonation of solvated formic acid was investigated theoretically with ab initio simulations. With the Car-Parrinello method, deprotonation and reprotonation by means of a proton wire were observed. The microscopics of these reactions were analyzed, and reveal the key role played by nearby water molecules in catalyzing the reactions. A constrained molecular dynamics calculation was carried out to estimate the dissociation free energy. Deprotonation of formic acid was further investigated with the recently developed metadynamics method using the formic acid oxygen coordination numbers as the collective variables. The determined free-energy landscape gives barriers similar to that obtained with the constrained free-energy calculation.

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页码：2325 / 2331

页数：7

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