论文标题
中间状态之间相关的自由能估计的变异得出的中间体
Variationally Derived Intermediates for Correlated Free Energy Estimates between Intermediate States
论文作者
论文摘要
从原子模拟基于原子模拟的基于原子模拟的准确性时，自由能差计算通常会提高准确性，当时从一系列中间平衡的热力学状态进行采样，这些状态弥合了两个感兴趣的状态之间的构型空间。出于效率的原因，通常使用相同的样品来计算这种中间体与两个相邻中间体的逐步差异。但是，此过程违反了不相关的估计的假设，这些估计值既可以得出中间状态的最佳序列和广泛使用的Bennett接受率（BAR）估计器。在这项工作中，通过变异方法，我们得出了中间状态的序列和相应的估计器，这些估计器具有最小的均衡误差，这些误差占了这些相关性并评估其准确性。
Free energy difference calculations based on atomistic simulations generally improve in accuracy when sampling from a sequence of intermediate equilibrium thermodynamic states that bridge the configuration space between two states of interest. For reasons of efficiency, usually the same samples are used to calculate the step-wise difference of such an intermediate to both adjacent intermediates. However, this procedure violates the assumption of uncorrelated estimates that is necessary to derive both the optimal sequence of intermediate states and the widely used Bennett acceptance ratio (BAR) estimator. In this work, via a variational approach, we derive the sequence of intermediate states and the corresponding estimator with minimal mean squared error that account for these correlations and assess its accuracy.
