A minimal thermodynamically consistent chemical oscillator
Inspired by the chemical reaction network considered the smallest system featuring a Hopf bifurcation and its reversible extension, we introduce an even more minimal reaction network that is thermodynamically consistent and exhibits autonomous oscillations under nonequilibrium driving. The model combines three features that are rarely realized simultaneously in compact oscillator networks: a chemically plausible structure restricted to uni- and bimolecular reactions, reversibility of such reactions, and analytical tractability. The system consists of three internal species coupled to two chemostatted species and still undergoes a supercritical Hopf bifurcation when a chemostat concentration is varied. To analyze the dynamics and thermodynamics near the onset of oscillations, we employ the mathematical technique of normal-form reduction, which allows obtaining a controlled irreversible approximation that preserves the leading phase-space structure of the full reversible network while enabling explicit calculations. This framework provides analytical access to the bifurcation structure and the leading contributions governing thermodynamic observables. Within this setting, we use the onset of oscillations to characterize the thermodynamic response of the system. In particular, we offer an analytical description of key thermodynamic quantities such as the semi-grand Gibbs free energy and the non-conservative work rate, which exhibit a kink-like discontinuity at the Hopf bifurcation. We thus provide an analytical description of a phenomenon previously characterized only through numerical simulations of more complex networks.
Authors
- Giulio Ragazzon (ORCID: https://orcid.org/0000-0002-7183-2985)
- Emanuele Penocchio (ORCID: https://orcid.org/0000-0002-1974-1613)
- Benedikt Remlein (ORCID: https://orcid.org/0000-0002-6048-3898)
- Beatrice Bartolomei (ORCID: https://orcid.org/0000-0003-4190-0040)
- Massimiliano Esposito
- Luca Monari
Institutions
- Centre National de la Recherche Scientifique (FR)
- University of Trieste (IT)
- University of Luxembourg (LU)
- Institut de Science et d'Ingénierie Supramoléculaires (FR)
- National Interuniversity Consortium of Materials Science and Technology (IT)
- Université de Strasbourg (FR)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2026-11-09
- DOI
- https://doi.org/10.1063/5.0357883
- Primary Topic
- Nonlinear Dynamics and Pattern Formation
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- European Commission
- Agence Nationale de la Recherche
- China Scholarship Council
- H2020 Marie Skłodowska-Curie Actions