English

Diffusion-entropy scaling across dimensions

Statistical Mechanics 2025-09-25 v2

Abstract

A quantitative relationship between the diffusion coefficient DD of a tagged particle in a liquid and the entropy SS of that liquid has long been sought, as it would allow entropy to be inferred directly from diffusion measurements and transport properties to be predicted from thermodynamic information. Here, we employ extensive computer simulations to independently compute both DD and SS for Lennard-Jones (LJ) liquids and for water across a wide range of thermodynamic state points. Our study covers two and three dimensions for both systems, and additionally explores one-dimensional confinement for water. We find that the ratio of diffusion coefficients between two states follows an almost perfect exponential dependence on their entropy difference. For LJ liquids, the exponential prefactor exhibits a pronounced dependence on dimensionality dd, consistent in trend but quantitatively distinct from theoretical predictions. In contrast, water shows a strikingly weak dimensionality dd dependence, deviating from theory, which we attribute to the dominant role of jump diffusion. Remarkably, the exponential diffusion-entropy relationship persists even when translational and rotational contributions to entropy are separated and considered individually. This robustness suggests that entropy provides a unifying measure governing particle mobility in liquids, largely independent of microscopic mechanisms or dimensional constraints.

Keywords

Cite

@article{arxiv.2505.11036,
  title  = {Diffusion-entropy scaling across dimensions},
  author = {Nayana Venkatareddy and Mohd Moid and Prabal K. Maiti and Biman Bagchi},
  journal= {arXiv preprint arXiv:2505.11036},
  year   = {2025}
}

Comments

10 pages, 5 figures

R2 v1 2026-06-28T23:35:39.752Z