Coarse graining photo-isomerization reactions: Thermodynamic consistency and implications for molecular ratchets

[en] 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, which 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, similar to 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.

Disciplines :

Chemistry

Author, co-author :

AVANZINI, Francesco ; University of Luxembourg > Faculty of Science, Technology and Medicine > Department of Physics and Materials Science > Team Massimiliano ESPOSITO

ESPOSITO, Massimiliano ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Physics and Materials Science (DPHYMS)

PENOCCHIO, Emanuele ; University of Luxembourg > Faculty of Science, Technology and Medicine > Department of Physics and Materials Science > Team Massimiliano ESPOSITO

External co-authors :

yes

Language :

English

Title :

Coarse graining photo-isomerization reactions: Thermodynamic consistency and implications for molecular ratchets

Publication date :

October 2025

Journal title :

Journal of Chemical Physics

Publisher :

AIP Publishing

Volume :

163

Issue :

Peer reviewed :

Peer reviewed

Available on ORBilu :

since 17 December 2025

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