Rognoni Alessandro, Conte Riccardo, Ceotto Michele
Dipartimento di Chimica, Università degli Studi di Milano Via Golgi 19 20133 Milano Italy
Chem Sci. 2020 Dec 18;12(6):2060-2064. doi: 10.1039/d0sc05785a.
Many efforts undertaken to study the solvation process have led to general theories that may describe mean properties, but are unable to provide a detailed understanding at the molecular level. Remarkably, the basic question of how many solvent molecules are necessary to solvate one solute molecule is still open. By exploring several water aggregates of increasing complexity, in this contribution we employ semiclassical spectroscopy to determine on quantum dynamical grounds the minimal network of surrounding water molecules to make the central one display the same vibrational features of liquid water. We find out that double-acceptor double-donor tetrahedral coordination constituting the standard picture is necessary but not sufficient, and that particular care must be reserved for the quantum description of the combination band due to the coupling of the central monomer bending mode with network librations. It is actually our ability to investigate the combination band with a quantum-derived approach that allows us to answer the titular question. The minimal structure eventually responsible for proper solvation is made of a total of 21 water molecules and includes two complete solvation shells, of which the whole first one is tetrahedrally coordinated to the central molecule.
为研究溶剂化过程所做的许多努力催生了一些通用理论,这些理论或许能够描述平均性质,但无法在分子层面提供详细的理解。值得注意的是,溶剂化一个溶质分子需要多少溶剂分子这个基本问题仍然没有答案。通过探索几个复杂度不断增加的水聚集体,在本论文中我们采用半经典光谱法,基于量子动力学原理来确定围绕中心水分子的最小水分子网络,以使中心水分子展现出与液态水相同的振动特征。我们发现,构成标准图景的双受体双供体四面体配位是必要条件,但并不充分,并且由于中心单体弯曲模式与网络平动的耦合,在对组合带进行量子描述时必须格外小心。实际上,正是我们运用量子衍生方法研究组合带的能力,使我们能够回答标题中的问题。最终负责恰当溶剂化的最小结构由总共21个水分子组成,包括两个完整的溶剂化壳层,其中整个第一个壳层以四面体方式与中心分子配位。