For solution-phase chemical reactions, the solvent is often considered simply as a medium to allow the reactants to encounter each other by diffusion. Although examples of direct solvent effects on molecular solutes exist, such as the compression of solute bonding electrons due to Pauli repulsion interactions, the solvent is not usually considered a part of the chemical species of interest. We show, using quantum simulations of Na₂, that when there are local specific interactions between a solute and solvent that are energetically on the same order as a hydrogen bond, the solvent controls not only the bond dynamics but also the chemical identity of the solute. In tetrahydrofuran, dative bonding interactions between the solvent and Na atoms lead to unique coordination states that must cross a free energy barrier of ~8 k_BT—undergoing a chemical reaction—to interconvert. Each coordination state has its own dynamics and spectroscopic signatures, highlighting the importance of considering the solvent in the identity of condensed-phase chemical systems.

对于溶液相化学反应，通常将溶剂简单地视为一种介质，以使反应物通过扩散彼此相遇。尽管存在直接的溶剂对分子溶质的影响的例子，例如由于泡利排斥相互作用而导致的溶质键合电子的压缩，但通常不将溶剂视为目标化学物质的一部分。我们展示了使用Na _2的量子模拟即，当溶质和溶剂之间存在与氢键具有相同能量级的局部特定相互作用时，溶剂不仅控制键的动力学，而且还控制溶质的化学特性。在四氢呋喃中，溶剂和Na原子之间的键合相互作用会导致独特的配位态，它们必须越过〜8 k _B T的自由能垒（ 正在进行化学反应）才能相互转化。每个配位态都有其自身的动力学和光谱特征，突出了在凝相化学系统的特性中考虑溶剂的重要性。