We present a novel molecular thermodynamic framework for the unambiguous assessment of the reliability of modeling approximations, their internal consistency, and the compliance with fundamental limiting behaviors in the description of solvation phenomena of species at infinite dilution in fluid systems over wide ranges of state conditions and solute-solvent intermolecular asymmetries. The proposed aprioristic approach does not rely on any type of regression technique; its accuracy rests on the theoretical validity and self-consistency of the underlying core solvation formalism and the first principles of chemical thermodynamics already established for model systems for which we have available exact formal results, and its application leads to the identification, as well as the isolation of the sources of modeling deficiencies. To that end, we (i) set the foundations for a rigorous description of the solvation behavior of solutes at infinite dilution at the microscopic and concomitant macroscopic levels, (ii) advance a set of thermodynamic limiting conditions as required constraints for any model of infinitely dilute solutions, (iii) identify the microscopic signatures of the solvation phenomena in terms of solute-induced perturbations of the solvent microstructure, and (iv) invoke an exact fluctuation formalism of solutions to assess the predictive capability of some current density-based models of aqueous non-electrolyte solutions. According to the findings of this analysis, we suggest a novel fully molecular-based alternative for the thermodynamic description of solutions at infinite dilution involving wide ranges of state conditions and solute-solvent intermolecular asymmetry, including the ideal gas solute and the solute behaving as another solvent species. This approach, which functions at a self-consistent integral plus derivative level, would automatically comply with all required thermodynamic constraints.

我们提出了一个新颖的分子热力学框架，用于明确评估建模近似的可靠性，它们的内部一致性以及在流体系统在状态状态和范围广泛的情况下无限稀释的物质的溶剂化现象的描述中基本限制行为的遵从性。溶质溶剂的分子间不对称性。提议的先验方法不依赖于任何类型的回归技术。它的准确性取决于潜在的核心溶剂化形式主义的理论有效性和自洽性，以及已经为模型系统建立的化学热力学的第一原理，对于这些系统我们可以获得确切的形式结果，其应用导致了鉴定，以及隔离建模缺陷的来源。为此，我们（i）为在微观和伴随的宏观水平上无限稀释的溶质的溶剂化行为的严格描述奠定了基础，（ii）提出了一组热力学极限条件，作为对任何无限稀溶液模型的必要约束，（iii）识别的溶剂化现象的微观特征在溶剂中的微结构的溶质诱导的扰动程度方面，（IV）调用溶液的精确波动形式来评估一些当前基于密度的非电解质水溶液模型的预测能力。根据分析的结果，我们提出了一种新颖的基于全分子的替代方法，用于无限稀释溶液的热力学描述，涉及广泛的状态条件和溶质-溶剂间不对称性，包括理想的气体溶质和表现为另一种性质的溶质。溶剂种类。这种以自洽积分加导数级起作用的方法将自动遵守所有要求的热力学约束。