Thermodynamic signatures of the period-doubling route to chemical chaos

Chemical reaction networks can evolve from stable oscillations to chaos through successive period doublings. We investigate general properties of entropy-production fluctuations near the onset of chaos and within the chaotic regime in reversible, well-mixed reaction networks. Near an isolated supercritical period-doubling bifurcation, we find a one-sided divergence of the diffusion constant with exponent one. For chaotic attractors satisfying the stated conditions, the entropy variance per unit volume grows exponentially when the macroscopic limit is taken first. Its exponential growth rate is 2λₘₐₓ, where λₘₐₓ is the largest Lyapunov exponent, implying a divergent diffusion constant. We also discuss the volume dependence of the fluctuations and the underlying physical mechanisms.