Perturbative Expansion in Reciprocal Space: Bridging Microscopic and Mesoscopic Descriptions of Molecular Interactions

被引:0
|
作者
Jin, Jaehyeok [1 ]
Reichman, David R. [1 ]
机构
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 2024年 / 128卷 / 04期
关键词
EQUILIBRIUM STATISTICAL-MECHANICS; DENSITY-FUNCTIONAL THEORY; EQUATION-OF-STATE; FORCE-FIELD; MODE EXPANSION; DIELECTRIC-CONSTANT; CLASSICAL FLUIDS; DYNAMICS; SIMULATION; WATER;
D O I
10.1021/acs.jpcb.3c06048
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Determining the Fourier representation of various molecular interactions is important for constructing density-based field theories from a microscopic point of view, enabling a multiscale bridge between microscopic and mesoscopic descriptions. However, due to the strongly repulsive nature of short-ranged interactions, interparticle interactions cannot be formally defined in Fourier space, which renders coarse-grained (CG) approaches in k-space somewhat ambiguous. In this paper, we address this issue by designing a perturbative expansion of pair interactions in reciprocal space. Our perturbation theory, starting from reciprocal space, elucidates the microscopic origins underlying zeroth-order (long-range attractions) and divergent repulsive interactions from higher order contributions. We propose a systematic framework for constructing a faithful Fourier-space representation of molecular interactions, capturing key structural correlations in various systems, including simple model systems and molecular CG models of liquids. Building upon the Ornstein-Zernike equation, our approach can be combined with appropriate closure relations, and to further improve the closure approximations, we develop a bottom-up parameterization strategy for inferring the bridge function from microscopic statistics. By incorporating the bridge function into the Fourier representation, our findings suggest a systematic, bottom-up approach to performing coarse-graining in reciprocal space, leading to the systematic construction of a bottom-up classical field theory of complex aqueous systems.
引用
收藏
页码:1061 / 1078
页数:18
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