Understanding solvation interactions is a key problem for many industrial fields: from pharmaceutical to material sciences. From a quantum mechanical viewpoint, two main difficulties arise: firstly, solvation takes place through weak interactions (hydrogen bonds, van der Waals interactions), which are inherently difficult to describe. Secondly, solvation properties are dynamic in nature, which means a proper statistical averaging is required to reproduce experimental properties. In this contribution, we dwell on the analysis of solute–solvent interactions by means of the averaged-NCI index, derived from an MD averaged picture of the electron density in the system. Firstly, we show how the approach enables to distinguish static vs labile and strong vs weak hydrogen bonds. Then, by means of this approach we are able to characterize the fact that the strength of hydrogen bonds with water solvent remains similar upon branching for aliphatic alcohols. On the contrary large differences have been observed between aliphatic alcohols and phenol derivatives. This statistical analysis of interactions is expected to be useful in the derivation of microscopic parameters for solute/solvent interactions.

了解溶剂化相互作用是许多工业领域的关键问题：从制药到材料科学。从量子力学的角度来看，出现了两个主要困难：首先，溶剂化是通过弱相互作用（氢键、范德华相互作用）发生的，这本身就很难描述。其次，溶剂化性质本质上是动态的，这意味着需要适当的统计平均来重现实验性质。在这个贡献中，我们专注于通过平均 NCI 指数分析溶质 - 溶剂相互作用，该指数源自系统中电子密度的 MD 平均图片。首先，我们展示了该方法如何能够区分静态与不稳定以及强与弱氢键。然后，通过这种方法，我们能够表征这样一个事实，即脂肪醇在支化时与水溶剂的氢键强度保持相似。相反，已经观察到脂肪醇和苯酚衍生物之间的巨大差异。这种相互作用的统计分析有望用于推导溶质/溶剂相互作用的微观参数。