论文标题

部分可观测时空混沌系统的无模型预测

A statistical perspective on microsolvation

论文作者

Rahbar, Mohammad, Stein, Christopher J.

论文摘要

缺乏确定与浴室相互作用的小系统平衡热力学特性的程序通常被视为常规统计力学的弱点。这样一个小系统的典型示例是溶质被明确的溶剂化外壳包围。解决此问题的一种方法是将小小的感兴趣的系统包装在一个明确的溶剂分子浴中,比系统本身大得多。显然,明确包含溶剂自由度显然受到可用的计算资源的限制。对此问题的潜在补救措施是一种微覆盖方法,其中仅考虑了少数明确的溶剂分子并被隐式溶剂浴所包围。尽管如此,对于常规的大规范蒙特卡洛方法,对溶剂自由度的采样具有挑战性,因为在小型系统热力学领域中不能定义溶剂分子的单一化学潜力。在这项工作中,提出了一个基于大规范合奏的统计热力学模型,该模型避免了常规的系统尺寸限制,并准确地表征了受浴室热力学约束的感兴趣系统的特性。我们将现有的微覆盖方法扩展到广义的多浴室“微统计”模型,并表明先前派生的方法是我们模型的限制。此处描述的框架是通用的,我们对Lennard-Jones模型流体进行数值验证。

The lack of a procedure to determine equilibrium thermodynamic properties of a small system interacting with a bath is frequently seen as a weakness of conventional statistical mechanics. A typical example for such a small system is a solute surrounded by an explicit solvation shell. One way to approach this problem is to enclose the small system of interest in a large bath of explicit solvent molecules, considerably larger than the system itself. The explicit inclusion of the solvent degrees of freedom is obviously limited by the available computational resources. A potential remedy to this problem is a microsolvation approach where only a few explicit solvent molecules are considered and surrounded by an implicit solvent bath. Still, the sampling of the solvent degrees of freedom is challenging with conventional grand canonical Monte Carlo methods, since no single chemical potential for the solvent molecules can be defined in the realm of small-system thermodynamics. In this work, a statistical thermodynamic model based on the grand canonical ensemble is proposed that avoids the conventional system size limitations and accurately characterizes the properties of the system of interest subject to the thermodynamic constraints of the bath. We extend an existing microsolvation approach to a generalized multi-bath "micro-statistical" model and show that the previously derived approaches result as a limit of our model. The framework described here is universal and we validate our method numerically for a Lennard-Jones model fluid.

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