Nonequilibrium thermodynamics of non-ideal chemical reaction networks

in Journal of Chemical Physics (2021), 154

All current formulations of nonequilibrium thermodynamics of open chemical reaction networks rely on the assumption of non-interacting species. We develop a general theory that accounts for interactions ... [more ▼]

All current formulations of nonequilibrium thermodynamics of open chemical reaction networks rely on the assumption of non-interacting species. We develop a general theory that accounts for interactions between chemical species within a mean-field approach using activity coefficients. Thermodynamic consistency requires that rate equations do not obey standard mass-action kinetics but account for the interactions with concentration dependent kinetic constants. Many features of the ideal formulations are recovered. Crucially, the thermodynamic potential and the forces driving non-ideal chemical systems out of equilibrium are identified. Our theory is general and holds for any mean-field expression of the interactions leading to lower bounded free energies. [less ▲]

Linear response in large deviations theory: a method to compute non-equilibrium distributions

in New J. Phys. (2021), 23(9), 093003

Strong current response to slow modulation: A metabolic case-study

in Journal of Chemical Physics (2020), 152(13), 134101

Thermodynamics of non-elementary chemical reaction networks

in New Journal of Physics (2020), 22(9), 093040

Chemical cloaking

in Physical Review. E. (2020), 101(6), 060102

Large deviations and dynamical phase transitions in stochastic chemical networks

in Journal of Chemical Physics (2019), 151(6),

Information Thermodynamics of Turing Patterns

in Physical Review Letters (2018)

e set up a rigorous thermodynamic description of reaction-diffusion systems driven out of equilibrium by time-dependent space-distributed chemostats. Building on the assumption of local equilibrium ... [more ▼]

e set up a rigorous thermodynamic description of reaction-diffusion systems driven out of equilibrium by time-dependent space-distributed chemostats. Building on the assumption of local equilibrium, nonequilibrium thermodynamic potentials are constructed exploiting the symmetries of the chemical network topology. It is shown that the canonical (resp. semigrand canonical) nonequilibrium free energy works as a Lyapunov function in the relaxation to equilibrium of a closed (resp. open) system and its variation provides the minimum amount of work needed to manipulate the species concentrations. The theory is used to study analytically the Turing pattern formation in a prototypical reaction-diffusion system, the one-dimensional Brusselator model, and to classify it as a genuine thermodynamic nonequilibrium phase transition. [less ▲]