Calculation of Molecular Volumes and Volumes of Activation Using Molecular Dynamics Simulations
Calculation of Molecular Volumes and Volumes of Activation Using Molecular Dynamics Simulations
复制标题
使用分子动力学模拟计算分子体积和活化体积
DOI：
10.1021/jp209088u
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发表时间：
2012
影响因子：
3.7
通讯作者：
N. Weinberg
中科院分区：
文献类型：
--
作者：
H. Wiebe;Jacob Spooner;N. Boon;E. Deglint;Essex Edwards;P. Dance;N. Weinberg
传统上，压力对反应速率的影响是用它们的压力导数来表示的，即活化量。在过渡态理论的框架内，这些活化体的体积可以用过渡态和反应物的体积之差来确定。因为反应物的体积很容易在实验上获得，所以活化体积提供了过渡态体积的直接测量，从而提供了对这些瞬时物种的独特一瞥。我们提出了一种基于分子动力学模拟计算分子体积的新方法。用该方法计算的非极性体系的分子体积和活化体体积与实验数据吻合较好。
Traditionally, the effects of pressure on the reaction rates are expressed in terms of their pressure derivatives, known as volumes of activation. Within the framework of transition-state theory, these volumes of activation can be identified with the difference in volumes of transition states and reactants. Because the volumes of reactants are readily available experimentally, the volumes of activation provide a direct measure of the transition-state volumes and thus a unique glimpse of these transient species. We propose a new approach toward calculating molecular volumes based on molecular dynamics simulations. Molecular volumes and volumes of activation for nonpolar systems calculated using this approach agree well with the experimental data.