论文标题
从非平衡方案中推断出平衡过渡速率
Inferring equilibrium transition rates from nonequilibrium protocols
论文作者
论文摘要
我们开发了一种理论，用于使用随机热力学的结果来推断受时间依赖力驱动的轨迹的平衡过渡速率。通过平衡分布函数和多余的耗散，将川崎关系应用于近似非平衡分布函数，我们制定了一个非平衡过渡状态理论，以估计由于非平衡方案而导致的平衡速率的速率提高。我们证明了我们理论的实用性，以在1和2维度中拉出谐波捕获的粒子以及一个半柔性的聚合物，并在3个维度中具有反应性接头。在所有情况下，我们都会发现，与基于贝尔定律的现象学方法相比，我们能够更有效地推断过渡率。我们预计我们的热力学方法将在分子模拟和力光谱实验中找到使用。
We develop a theory for inferring equilibrium transition rates from trajectories driven by a time dependent force using results from stochastic thermodynamics. Applying the Kawasaki relation to approximate the nonequilibrium distribution function in terms of the equilibrium distribution function and the excess dissipation, we formulate a nonequilibrium transition state theory to estimate the rate enhancement over the equilibrium rate due to the nonequilibrium protocol. We demonstrate the utility of our theory in examples of pulling of harmonically trapped particles in 1 and 2 dimensions, as well as a semi-flexible polymer with a reactive linker in 3 dimensions. In all cases we find that we are able to infer the transition rates more effectively than phenomenological approaches based on Bell's law. We expect our thermodynamic approach will find use in both molecular simulation and force spectroscopy experiments.
