Physical Modeling of Aqueous Solvation
Physical Modeling of Aqueous Solvation
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DOI：
10.1007/s10955-011-0232-9
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发表时间：
2011-10-01
影响因子：
1.6
通讯作者：
Dill, Ken A.
中科院分区：
文献类型：
--
作者：
Fennell, Christopher J.;Dill, Ken A.
我们考虑水中溶剂化分子的自由能。计算建模通常涉及详细的显式溶剂模拟或基于隐式连续统近似或可加性假设的更快计算。这些更简单的方法常常会忽略实验数据中存在的微观物理细节和非可加性。我们回顾了显式溶剂模型，该模型确定了更简单方法中错误的物理基础。一个问题是两个取代基之间共享的水分子的行为通常与每个取代基周围的水分子的行为不同。非加和性的一种表现是水中的溶剂化自由能不仅取决于表面积或体积，还取决于其他特性，例如表面曲率。我们还描述了一种新的计算方法，称为半显式组装，旨在修复这些缺陷并捕获更多显式水模型的物理原理，但计算效率接近隐式溶剂模型的计算效率。
We consider the free energies of solvating molecules in water. Computational modeling usually involves either detailed explicit-solvent simulations, or faster computations, which are based on implicit continuum approximations or additivity assumptions. These simpler approaches often miss microscopic physical details and non-additivities present in experimental data. We review explicit-solvent modeling that identifies the physical bases for the errors in the simpler approaches. One problem is that water molecules that are shared between two substituent groups often behave differently than waters around each substituent individually. One manifestation of non-additivities is that solvation free energies in water can depend not only on surface area or volume, but on other properties, such as the surface curvature. We also describe a new computational approach, called Semi-Explicit Assembly, that aims to repair these flaws and capture more of the physics of explicit water models, but with computational efficiencies approaching those of implicit-solvent models.