Loop expansion in polymer field theory: application to phase separation
Abstract
Liquid-liquid phase separation underlies phenomena ranging from protein condensate formation to the phase coexistence of synthetic polymers. Although the random phase approximation (RPA) is widely used to predict such phase behavior, its quantitative accuracy for binodals of polymer solutions, particularly outside the high-density regime, remains incompletely characterized. Here, we develop a field-theoretic loop expansion in homopolymer systems by identifying the inverse polymer density ρ−1 as the Planck constant ℏ in quantum field theory. We calculate the leading-order and next-to-leading-order corrections to the RPA free energy, denoted as RPA+ and RPA++, respectively. Testing the binodal predicted by the RPA+ against molecular dynamics simulations of bead-spring chains with Gaussian pair interactions, we find that the RPA+ qualitatively improves the dilute-phase coexistence density over the RPA, while the critical point error remains comparable to that of the RPA. Our results establish the loop expansion as a systematic route for refining the RPA-based binodal predictions for polymer phase separation.
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BibTeX
@misc{kawana2026loop,
title = {{Loop expansion in polymer field theory: application to phase separation}},
author = {Kiyoharu Kawana and Kyosuke Adachi},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2605.01261},
eprint = {2605.01261},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2605.01261},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Loop expansion in polymer field theory: application to phase separation
AU - Kiyoharu Kawana
AU - Kyosuke Adachi
PY - 2026
DA - 2026/09/11
PB - arXiv
DO - 10.48550/arxiv.2605.01261
UR - https://arxiv.org/abs/2605.01261
AB - Liquid-liquid phase separation underlies phenomena ranging from protein condensate formation to the phase coexistence of synthetic polymers. Although the random phase approximation (RPA) is widely used to predict such phase behavior, its quantitative accuracy for binodals of polymer solutions, particularly outside the high-density regime, remains incompletely characterized. Here, we develop a field-theoretic loop expansion in homopolymer systems by identifying the inverse polymer density ρ^−1 as the Planck constant ℏ in quantum field theory. We calculate the leading-order and next-to-leading-order corrections to the RPA free energy, denoted as RPA+ and RPA++, respectively. Testing the binodal predicted by the RPA+ against molecular dynamics simulations of bead-spring chains with Gaussian pair interactions, we find that the RPA+ qualitatively improves the dilute-phase coexistence density over the RPA, while the critical point error remains comparable to that of the RPA. Our results establish the loop expansion as a systematic route for refining the RPA-based binodal predictions for polymer phase separation.
ER -