论文标题
偏斜的热力学几何形状和最佳自由能估计
Skewed Thermodynamic Geometry and Optimal Free Energy Estimation
论文作者
论文摘要
自由能差异是物理，化学和生物学的中心含量。我们开发了提高自由能估计器的精度和准确性的设计原理，该原理具有潜在的应用于筛查目标药物发现的应用。具体而言，通过利用时间转换协议对的工作统计数据之间的联系，我们为多余工作的矩进行了接近平衡的近似值，并分析了对标准非平衡自由能估计器的精确性和准确性的主要贡献。在线性响应中，最小隔离方案遵循由Stokes的摩擦张量引起的Riemannian指标的测量学。我们发现下一阶贡献是由等级3上的张量引起的，该张量偏向几何结构，因此最小散落方案遵循广义立方体鳍度量指标的大地测量。因此，在平衡的接近均衡器张量确定了对双向自由能估计器偏置的领先贡献。
Free energy differences are a central quantity of interest in physics, chemistry, and biology. We develop design principles that improve the precision and accuracy of free energy estimators, which has potential applications to screening for targeted drug discovery. Specifically, by exploiting the connection between the work statistics of time-reversed protocol pairs, we develop near-equilibrium approximations for moments of the excess work and analyze the dominant contributions to the precision and accuracy of standard nonequilibrium free-energy estimators. Within linear response, minimum-dissipation protocols follow geodesics of the Riemannian metric induced by the Stokes' friction tensor. We find the next-order contribution arises from the rank-3 supra-Stokes' tensor that skews the geometric structure such that minimum-dissipation protocols follow geodesics of a generalized cubic Finsler metric. Thus, near equilibrium the supra-Stokes' tensor determines the leading-order contribution to the bias of bidirectional free-energy estimators.
