Renormalized site density functional theory

TL;DR

This paper introduces a renormalized site density functional theory that improves the modeling of inhomogeneous molecular liquids by decoupling intra- and inter-molecular interactions using dual space methodology, leading to more accurate results.

Contribution

It develops a dual space approach with renormalized parameters to better describe molecular liquids, addressing limitations of existing SDFT methods.

Findings

Renormalization improves accuracy of SDFT for diatomic liquids.

Decoupling interaction scales enhances modeling flexibility.

Effective fluid mixture analogy simplifies analysis.

Abstract

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.