A route to the thermodynamics of colloid-polymer mixtures from structural information
Abstract
Liquid-state theory provides a fundamental connection between microscopic structure and macroscopic thermodynamic behaviour. Here, we develop a framework for predicting thermodynamics and phase behaviour directly from structural correlations, using either radial distribution functions or static structure factors as input. The approach constructs a free-energy functional from structural information obtained at a single thermodynamic state point, without requiring explicit knowledge of the underlying interaction potentials. This circumvents a central difficulty in modelling complex fluids, for which effective interactions are often unknown or rely on approximations. We demonstrate the framework for a range of model fluids, including colloidal and colloid--polymer systems, with predictions in good agreement with molecular simulation data. The results show that structural information at a single state point can provide sufficient information to predict the broader thermodynamic response of a system. This establishes a route toward inferring phase behaviour directly from experimentally measured structure, even when the microscopic interactions are not known a priori.
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BibTeX
@misc{varma2026route,
title = {{A route to the thermodynamics of colloid-polymer mixtures from structural information}},
author = {Vikki Anand Varma and Andrew J. Archer and Alberto Scacchi},
howpublished = {arXiv},
year = {2026},
month = aug,
doi = {10.48550/arxiv.2608.29124},
eprint = {2608.29124},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2608.29124},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - A route to the thermodynamics of colloid-polymer mixtures from structural information
AU - Vikki Anand Varma
AU - Andrew J. Archer
AU - Alberto Scacchi
PY - 2026
DA - 2026/08/29
PB - arXiv
DO - 10.48550/arxiv.2608.29124
UR - https://arxiv.org/abs/2608.29124
AB - Liquid-state theory provides a fundamental connection between microscopic structure and macroscopic thermodynamic behaviour. Here, we develop a framework for predicting thermodynamics and phase behaviour directly from structural correlations, using either radial distribution functions or static structure factors as input. The approach constructs a free-energy functional from structural information obtained at a single thermodynamic state point, without requiring explicit knowledge of the underlying interaction potentials. This circumvents a central difficulty in modelling complex fluids, for which effective interactions are often unknown or rely on approximations. We demonstrate the framework for a range of model fluids, including colloidal and colloid--polymer systems, with predictions in good agreement with molecular simulation data. The results show that structural information at a single state point can provide sufficient information to predict the broader thermodynamic response of a system. This establishes a route toward inferring phase behaviour directly from experimentally measured structure, even when the microscopic interactions are not known a priori.
ER -