Metastability and Nucleation in Chemical Systems with Multiple Steady States
In 1971 Prigogine and Nicolis  suggested that the transitions between non-equilibrium chemical steady states are induced from local fluctuations by a nucleation process and exhibit metastability phenomena. In this frame, the chemical bistability appears as a close analog to the Van der Waals isotherm problem of the first-order equilibrium transitions . The two deterministic steady states can only coexit, when fluctuations are included, for a single set of the constraints (coexistence point). Elsewhere, the metastable state, say Em, converts into the stable state, say Es, as soon as a spontaneous fluctuation into state Es is large enough to spread to the whole system. The existence of a critical size for this fluctuation is related to the competition between the bulk nonlinear reactive processes and the diffusion processes which break and dilute the fluctuation, but are localized only to the surface between Em and Es. So the last dominate only for small fluctuations. When this critical size is large, near the coexistence point, or for fast diffusion, the life time τ of Em is long and Em appears as stable. When this size is small, far away from the coexistence point on the metastable branch, or for slow diffusion, τ is small, the transition occurs at once and Em appears to be unstable.
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