论文标题
从微型恒温器的一阶相变的动力学
Kinetics of first-order phase transitions from microcanonical thermostatistics
论文作者
论文摘要
自从Van't Hoff和Arrhenius提出了他们著名的费率理论以来，已经过去了一个多世纪，但是分子系统的温度依赖性相过渡动力学仍然存在难以捉摸的方面。在这里，我提出了一个基于微型恒温器的理论，该理论为所有速率常数（包括正向和反向速率常数，平衡常数和成核速率）建立了简单而直接的温度依赖性。通过考虑一个通用模型，该模型在接近一阶相变的区域中模仿分子系统的微域温度，我获得了动力学和热力学物理量之间的无形关系，这些关系通过随机模拟验证。此外，速率理论应用于从蛋白质折叠和冰核实验中获得的结果，表明此处得出的表达式可用于描述各种分子系统的实验数据。
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.
