一种适用于跨长度尺度溶剂化的经典密度泛函理论
A classical density functional theory for solvation across length scales
AI总结：
本研究提出一种基于经典密度泛函理论的新方法，以密度场慢变分量构建自由能泛函，可跨长度尺度精确描述非极性溶质溶剂化，数值更简便、适用范围更广，还能捕捉温度依赖性并覆盖远超分子模拟的尺度。
摘要：
多尺度建模的核心目标是利用薛定谔方程的结果，预测远超出典型分子关联长度尺度的现象。在本研究中，我们提出了一种植根于经典密度泛函理论（cDFT）的新方法，能够精确描述非极性溶质在跨长度尺度下的溶剂化行为。我们的方法基于Lum-Chandler-Weeks（LCW）疏水性理论[K. Lum等人，J. Phys. Chem. B 103, 4570 (1999)]，通过构建以密度场的慢变分量为参考的自由能泛函实现。从实用角度看，我们提出的理论在数值上更简单，且比LCW理论更易推广到具有软核排斥作用的溶质。此外，通过评估局部可压缩性及其临界标度行为，我们证明了这种类LCW的cDFT方法包含临界干燥的物理机制，而临界干燥已被近期理论强调为疏水性的一个核心方面。由于我们的方法以均匀流体的两体直接关联函数和液-气表面张力为参数化基础，因此可以直接捕捉溶剂化的温度依赖性。此外，我们还利用该理论在第一性原理层面描述了溶剂化过程，其适用的长度尺度远远超过了分子模拟可及的范围。
英文摘要：
A central aim of multiscale modeling is to use results from the Schrödinger Equation to predict phenomenology on length scales that far exceed those of typical molecular correlations. In this work, we present a new approach rooted in classical density functional theory (cDFT) that allows us to accurately describe the solvation of apolar solutes across length scales. Our approach builds on the Lum-Chandler-Weeks (LCW) theory of hydrophobicity [K. Lum et al., J. Phys. Chem. B 103, 4570 (1999)] by constructing a free energy functional that uses a slowly-varying component of the density field as a reference. From a practical viewpoint, the theory we present is numerically simpler and generalizes to solutes with soft-core repulsion more easily than LCW theory. Furthermore, by assessing the local compressibility and its critical scaling behavior, we demonstrate that our LCW-style cDFT approach contains the physics of critical drying, which has been emphasized as an essential aspect of hydrophobicity by recent theories. As our approach is parameterized on the two-body direct correlation function of the uniform fluid and the liquid-vapor surface tension, it straightforwardly captures the temperature dependence of solvation. Moreover, we use our theory to describe solvation at a first-principles level, on length scales that vastly exceed what is accessible to molecular simulations.
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