AB-INITIO MOLECULAR-DYNAMICS SIMULATION OF THE SOLVATION AND TRANSPORT OF H3O+ AND OH- IONS IN WATER

被引：549

作者：

TUCKERMAN, M ^{[1
]}

LAASONEN, K ^{[1
]}

SPRIK, M ^{[1
]}

PARRINELLO, M ^{[1
]}

机构：

[1] IBM CORP,DIV RES,ZURICH RES LAB,CH-8803 RUSCHLIKON,SWITZERLAND

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 16期

关键词：

D O I：

10.1021/j100016a003

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：

Applying the ab initio molecular dynamics method, we have studied the solvation and dynamics of an excess proton and a proton hole in liquid water. We find for the H3O+ ion a dynamic solvation complex which continuously fluctuates between a (H5O2)(+) and (H9O4)(+) structure as a result of proton transfer. The results of the simulation strongly suggest that the rate-limiting step for the migration of the excess proton is the concerted dynamics of the second solvation shell hydrogen bonded to the ligand H2O molecules. The OH- ion has a predominantly planar 4-fold coordination. Proton transfer is only observed when this (H9O5)(-) complex is transformed into a tetrahedral (H7O4)(-) configuration. The formation of this more open complex determines the OH- diffusion rate.

引用

页码：5749 / 5752

页数：4