论文标题

重新归一化的位点密度功能理论

Renormalized site density functional theory

论文作者

Chuev, Gennady N., Fedotova, Marina V., Valiev, Marat

论文摘要

位点密度功能理论(SDFT)为不均匀分子液体的统计力学分析提供了严格的框架。这些系统的关键定义特征是存在两个非常不同的相互作用量表(分子内和分子间),因此对这两种效应的正确描述对于计算的准确性至关重要。当前的SDFT应用程序利用两个相互作用基序都使用相同的近似方案,从而对结果产生负面影响。这项工作中使用的双空间方法可以通过评估传统现场表示中的部分相互作用的灵活性来减轻此问题。对于分子液体,这转化为分子间相互作用的保留密度表示,但通过更合适的常规场方法描述了僵硬的分子内剩余方法。这打开了对两个相互作用量表的分析的方法 - 这项工作在这项工作中进一步开发的思想是对分子间相互作用的均匀参考近似。我们证明,通过定义新的集体变量,可以转化原始分子液体系统在分子间水平上的行为,以类似于有效的简单流体混合物的行为。后者通过重新归一化的相互作用参数与分子内尺度有关。我们说明了几种类型的双原子液体的重新归一化过程,这表明这种方法治愈了现有SDFT方法的许多缺点。

Site density functional theory (SDFT) provides a rigorous framework for statistical mechanics analysis of inhomogeneous molecular liquids. The key defining feature of these systems is the presence of two very distinct interactions scales (intra- and inter-molecular), and as such proper description of both effects is critical to the accuracy of the calculations. Current SDFT applications utilize the same approximation scheme for both interaction motifs, which negatively impacts the results. Dual space methodology, used in this work, alleviates this issue by providing the flexibility of evaluating part of the interactions in traditional field representation. For molecular liquid this translates into retaining density representation for inter-molecular interactions but describing stiff intra-molecular remainder by more appropriate conventional field based methods. This opens the way to decouple analysis of the two interactions scales - the idea which is developed further in this work for the case of homogeneous reference approximation of inter-molecular interactions. We demonstrate that by defining new collective variables, the behavior of the original molecular liquid system at the inter-molecular level can be transformed to resemble that of an effective simple fluid mixture. The latter is linked to intra-molecular scale through renormalized interaction parameters. We illustrate this renormalization procedure for several types of diatomic liquids, showing that this approach cures many of the shortcomings of existing SDFT methods.

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