Laboratory of Physical Chemistry, ETH Zürich, Zürich, Switzerland.
J Comput Chem. 2020 May 5;41(12):1144-1155. doi: 10.1002/jcc.26161. Epub 2020 Feb 6.
Solvation is a notoriously difficult and nagging problem for the rigorous theoretical description of chemistry in the liquid phase. Successes and failures of various approaches ranging from implicit solvation modeling through dielectric continuum embedding and microsolvated quantum chemical modeling to explicit molecular dynamics highlight this situation. Here, we focus on quantum chemical microsolvation and discuss an explicit conformational sampling ansatz to make this approach systematic. For this purpose, we introduce an algorithm for rolling and automated microsolvation of solutes. Our protocol takes conformational sampling and rearrangements in the solvent shell into account. Its reliability is assessed by monitoring the evolution of the spread and average of the observables of interest.
溶剂化对于液相中化学的严格理论描述是一个众所周知的难题和难题。从隐式溶剂化建模到介电连续体嵌入和微溶剂化量子化学建模再到显式分子动力学等各种方法的成功和失败都突出了这种情况。在这里，我们专注于量子化学微溶剂化，并讨论了一种显式构象采样假设，以使该方法系统化。为此，我们引入了一种用于滚动和自动溶剂化溶质的算法。我们的方案考虑了溶剂壳中的构象采样和重排。通过监测感兴趣的观测值的分布和平均值的演变来评估其可靠性。
