A classical density functional theory for solvation across length scales
arxiv(2024)
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 and Weeks (LCW) theory of hydrophobicity [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, we
also provide two important conceptual insights. First, the coarse-graining of
the density field emerges naturally and justifies a coarse-graining length much
smaller than the molecular diameter of water. Second, 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
theory 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.
更多查看译文
AI 理解论文
溯源树
样例
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要