Stochastic models of firstorder nonequilibrium phase transitions in chemical reactions

The steady states of a simple nonlinear chemical system kept far from equilibrium are analyzed. A standard macroscopic analysis shows that the nonlinearity introduces an instability causing a transition analogous to a thermodynamic first-order phase transition. Near this transition the system exhibits hysteresis between two alternative steady states. Fluctuations are introduced into this model using a stochastic master equation. The solution of this master equation is unique, preventing two alternative exactly stable states. However, a quasi-hysteresis occurs involving transitions between alternative metastable steady states on a time scale that is longer than that of the fluctuations around the mean steady state values by a factor of the formeΔφ, where Δø is the height of a generalized thermodynamic potential barrier between the two states. In the thermodynamic limit this time scale tends to infinity and we have essentially two alternative stable steady states.

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