远边界对带电粒子溶剂化的影响
The Influence of Distant Boundaries on the Solvation of Charged Particles
摘要：
库仑势的长程性质要求在确定带电溶质的溶剂化自由能时适当考虑甚至遥远的静电边界的影响。我们引入了对溶质充电时自由能变化的精确重写，显式隔离了这些边界的贡献，并量化了不同边界对自由能的影响。我们证明了适当参考的静电势的真空，通过几个简单的模型电荷分布的研究，我们可以隔离的边界，可以很容易地在计算机模拟分子系统的分析贡献的重要性和优势。最后，我们强调，体介电相的恒定电位-贝特电位-不能有助于一个单一的带电溶质的溶剂化热力学时，溶剂和溶质的电荷分布不重叠在相关的配置。但是当单个溶质的电荷分布可以与溶剂分子的分子内电荷分布重叠时，例如在电子全息中的情况，当与实验比较时，需要Bethe势。我们的工作也可以提供洞察力的有效性“额外的热力学假设”传统的单离子溶剂化自由能的实验测定过程中。
英文摘要：
The long-ranged nature of the Coulomb potential requires a proper accounting for the influence of even distant electrostatic boundaries in the determination of the solvation free energy of a charged solute. We introduce an exact rewriting of the free energy change upon charging a solute that explicitly isolates the contribution from these boundaries and quantifies the impact of the different boundaries on the free energy. We demonstrate the importance and advantages of appropriately referencing the electrostatic potential to that of the vacuum through the study of several simple model charge distributions, for which we can isolate an analytic contribution from the boundaries that can be readily evaluated in computer simulations of molecular systems. Finally, we highlight that the constant potential of the bulk dielectric phase - the Bethe potential - cannot contribute to the solvation thermodynamics of a single charged solute when the charge distributions of the solvent and solute do not overlap in relevant configurations. But when the charge distribution of a single solute can overlap with the intramolecular charge distribution of solvent molecules, as is the case in electron holography, for example, the Bethe potential is needed when comparing to experiment. Our work may also provide insight into the validity of "extra thermodynamic assumptions" traditionally made during the experimental determination of single ion solvation free energies.
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