Computing Equilibrium Free Energies Using Non-Equilibrium Molecular Dynamics
Computing Equilibrium Free Energies Using Non-Equilibrium Molecular Dynamics
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DOI：
10.3390/e16010041
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发表时间：
2014-01-01
期刊：
影响因子：
2.7
通讯作者：
Hummer, Gerhard
中科院分区：
文献类型：
--
作者：
Dellago, Christoph;Hummer, Gerhard
正如Jarzynski所示，平衡态之间的自由能差可以用非平衡变换过程中对系统所做的功的统计来表示。这个精确的结果，以及相关的克鲁克斯波动定理，提供了从快速切换分子动力学模拟计算自由能差的基础，其中外部参数以有限的速率变化，驱动系统远离平衡。在这篇文章中，我们首先简要回顾Jarzynski身份和Crooks波动定理，然后调查各种算法建立在这些关系。我们特别注意这些方法的统计效率，并讨论其实施和结果分析中出现的实际问题。
As shown by Jarzynski, free energy differences between equilibrium states can be expressed in terms of the statistics of work carried out on a system during non-equilibrium transformations. This exact result, as well as the related Crooks fluctuation theorem, provide the basis for the computation of free energy differences from fast switching molecular dynamics simulations, in which an external parameter is changed at a finite rate, driving the system away from equilibrium. In this article, we first briefly review the Jarzynski identity and the Crooks fluctuation theorem and then survey various algorithms building on these relations. We pay particular attention to the statistical efficiency of these methods and discuss practical issues arising in their implementation and the analysis of the results.