Can water polarizability be ignored in hydrogen bond kinetics?

被引:193
作者
Xu, HF
Stern, HA
Berne, BJ
机构
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
[2] Columbia Univ, Ctr Biomol Simulat, New York, NY 10027 USA
关键词
D O I
10.1021/jp013426o
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 kinetics of forming and breaking water-water hydrogen bonds in neat water, an aqueous solution of ethane, and an aqueous solution of NaCl are studied by molecular dynamics simulations. We compare nonpolarizable and polarizable water models to elucidate the effect of water's polarizability on hydrogen bonds. We find that polarizability strengthens the hydrogen bonds and increases the hydrogen bond relaxation time by a factor of between 50% and 100%. The Gibbs energy of activation for breaking hydrogen bonds is similar to0.2 kcal(.)mol(-1) higher for the polarizable water model. Polarizability also causes the rate of forming and breaking hydrogen bonds to be more dependent on the local environment.
引用
收藏
页码:2054 / 2060
页数:7
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