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Kinetics of first-order phase transitions from microcanonical thermostatistics

More than a century has passed since van't Hoff and Arrhenius formulated their celebrated rate theories, but there are still elusive aspects in the temperature-dependent phase transition kinetics of molecular systems. Here I present a theory based on microcanonical thermostatistics that establishes a simple and direct temperature dependence for all rate constants, including the forward and the reverse rate constants, the equilibrium constant, and the nucleation rate. By considering a generic model that mimic the microcanonical temperature of molecular systems in a region close to a first-order phase transition, I obtain shape-free relations between kinetics and thermodynamics physical quantities which are validated through stochastic simulations. Additionally, the rate theory is applied to results obtained from protein folding and ice nucleation experiments, demonstrating that the expressions derived here can be used to describe the experimental data of a wide range of molecular systems.