Study of solvent effects by means of averaged solvent electrostatic potentials obtained from molecular dynamics data
Study of solvent effects by means of averaged solvent electrostatic potentials obtained from molecular dynamics data
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通过从分子动力学数据获得的平均溶剂静电势研究溶剂效应
DOI：
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发表时间：
1997
影响因子：
3
通讯作者：
F. D. Valle
中科院分区：
文献类型：
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作者：
M. L. Sánchez;M. Aguilar;F. D. Valle
我们介绍了一种研究溶剂效应的新方法的理论和实现。在从头算水平上计算的溶质的电子结构是在周围介质存在的情况下得到的。我们采用平均场理论，其中溶剂响应是通过选择点电荷来描述的，所选的点电荷重现了从分子动力学数据计算的溶剂静电势的平均值。这样，完全溶剂势可以被引入到溶质哈密顿量中，而不需要利用溶质-溶剂势的单中心多重展开。在所提出的方法中，只需要进行一次量子计算，并且可以很容易地包括大量的组态，使得计算在统计上具有重要意义。我们发现，尽管溶剂引起的溶质电荷分布有很大的波动，但平均场理论很好地再现了甲酰胺和水分子在水溶液中的能级和性质。©1997 John Wiley&Sons，Inc.
We present the theory and implementation of a new approach for studying solvent effects. The electronic structure of the solute, calculated at the ab initio level, is obtained in the presence of the surrounding medium. We employ a mean field theory in which the solvent response is described by means of point charges chosen in such a way that they reproduce the average value of the solvent electrostatic potential calculated from molecular dynamics data. In this way, the complete solvent potential can be introduced into the solute Hamiltonian without making use of a one‐center multiple expansion of the solute‐solvent potential. In the proposed method, only one quantum calculation has to be performed and a great number of configurations can easily be included making the calculation statistically significant. We show that, despite the large fluctuations in the solute charge distribution induced by the solvent, the proposed mean field theory adequately reproduces the energetics and properties of formamide and water molecules in aqueous solution. © 1997 by John Wiley & Sons, Inc.