Coarse Graining Photo-Isomerization Reactions: Thermodynamic Consistency and Implications for Molecular Ratchets

Fuente: arXiv
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Auteurs principaux: Avanzini, Francesco, Esposito, Massimiliano, Penocchio, Emanuele
Format: Preprint
Publié: 2025
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author Avanzini, Francesco
Esposito, Massimiliano
Penocchio, Emanuele
author_facet Avanzini, Francesco
Esposito, Massimiliano
Penocchio, Emanuele
contents We formulate thermodynamically consistent coarse-graining procedures for molecular systems undergoing thermally and photo-induced transitions: starting from elementary vibronic transitions, we derive effective photo-isomerization reactions interconverting ground-state species. Crucially, the local detailed balance condition, that constrains reaction kinetics to thermodynamics, remains satisfied throughout the coarse-graining procedures. It applies to the effective photo-isomerization reactions just as it does to the elementary vibronic transitions. We then demonstrate that autonomous photo-driven molecular ratchets operate via the same fundamental mechanism as chemically driven ones. Because the local detailed balance remains satisfied, autonomous photo-driven molecular ratchets, like chemically driven ones, operate exclusively through an information ratchet mechanism. This reveals that their design and optimization should prioritize molecular properties governing the information ratchet mechanism, rather than those influencing energetic bias.
format Preprint
id arxiv_https___arxiv_org_abs_2507_08453
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Coarse Graining Photo-Isomerization Reactions: Thermodynamic Consistency and Implications for Molecular Ratchets
Avanzini, Francesco
Esposito, Massimiliano
Penocchio, Emanuele
Statistical Mechanics
Chemical Physics
We formulate thermodynamically consistent coarse-graining procedures for molecular systems undergoing thermally and photo-induced transitions: starting from elementary vibronic transitions, we derive effective photo-isomerization reactions interconverting ground-state species. Crucially, the local detailed balance condition, that constrains reaction kinetics to thermodynamics, remains satisfied throughout the coarse-graining procedures. It applies to the effective photo-isomerization reactions just as it does to the elementary vibronic transitions. We then demonstrate that autonomous photo-driven molecular ratchets operate via the same fundamental mechanism as chemically driven ones. Because the local detailed balance remains satisfied, autonomous photo-driven molecular ratchets, like chemically driven ones, operate exclusively through an information ratchet mechanism. This reveals that their design and optimization should prioritize molecular properties governing the information ratchet mechanism, rather than those influencing energetic bias.
title Coarse Graining Photo-Isomerization Reactions: Thermodynamic Consistency and Implications for Molecular Ratchets
topic Statistical Mechanics
Chemical Physics
url https://arxiv.org/abs/2507.08453