Shenfeld Daniel K, Xu Huafeng, Eastwood Michael P, Dror Ron O, Shaw David E
D E Shaw Research, New York, New York 10036, USA.
Phys Rev E Stat Nonlin Soft Matter Phys. 2009 Oct;80(4 Pt 2):046705. doi: 10.1103/PhysRevE.80.046705. Epub 2009 Oct 19.
In computational thermodynamics, a sequence of intermediate states is commonly introduced to connect two equilibrium states. We consider two cases where the choice of intermediate states is particularly important: minimizing statistical error in free-energy difference calculations and maximizing average acceptance probabilities in replica-exchange simulations. We derive bounds for these quantities in terms of the thermodynamic distance between the intermediates, and show that in both cases the intermediates should be chosen as equidistant points along a geodesic connecting the end states.
在计算热力学中，通常引入一系列中间态来连接两个平衡态。我们考虑两种中间态选择尤为重要的情况：在自由能差计算中最小化统计误差以及在副本交换模拟中最大化平均接受概率。我们根据中间态之间的热力学距离推导出这些量的界限，并表明在这两种情况下，中间态都应沿着连接终态的测地线选为等距点。
