Dynamic correlations in a polar fluid: confronting stochastic density functional theory to simulations

TL;DR

This paper develops a stochastic density functional theory to model polarization dynamics in polar fluids, specifically the Stockmayer fluid, and validates it against simulations, revealing strengths and limitations in describing collective polarization fluctuations.

Contribution

The paper introduces a linearized stochastic density functional theory for dipolar fluids and demonstrates its effectiveness in capturing polarization dynamics compared to simulations.

Findings

SDFT accurately predicts longitudinal polarization fluctuations.

Transverse fluctuations are underestimated without correction.

Incorporating the Kirkwood factor improves agreement with simulations.

Abstract

Understanding the dynamic behavior of polar fluids is essential for modeling complex systems such as electrolytes and biological media. In this work, we develop and apply a Stochastic Density Functional Theory (SDFT) framework to describe the polarization dynamics in the Stockmayer fluid, a prototypical model of dipolar liquids consisting of Lennard-Jones particles with embedded point dipoles. Starting from the overdamped Langevin dynamics of dipolar particles, we derive analytical expressions for the intermediate scattering functions and dynamic structure factors of the longitudinal and transverse components of the polarization field, within linearized SDFT. To assess the theory's validity, we compare its predictions with results from Brownian Dynamics simulations of the Stockmayer fluid. We find that SDFT captures the longitudinal polarization fluctuations accurately, while transverse fluctuations are underestimated due to the neglect of dipolar correlations. By incorporating the Kirkwood factor into a modified SDFT, we recover quantitative agreement for both components across a range of dipole strengths. This study highlights the utility of SDFT as a coarse-grained description of polar fluid dynamics and provides insights into the role of collective effects in polarization relaxation.