Stroet Martin, Koziara Katarzyna B, Malde Alpeshkumar K, Mark Alan E
School of Chemistry and Molecular Biosciences, University of Queensland , St. Lucia, Queensland 4072, Australia.
J Chem Theory Comput. 2017 Dec 12;13(12):6201-6212. doi: 10.1021/acs.jctc.7b00800. Epub 2017 Nov 21.
A general method for parametrizing atomic interaction functions is presented. The method is based on an analysis of surfaces corresponding to the difference between calculated and target data as a function of alternative combinations of parameters (parameter space mapping). The consideration of surfaces in parameter space as opposed to local values or gradients leads to a better understanding of the relationships between the parameters being optimized and a given set of target data. This in turn enables for a range of target data from multiple molecules to be combined in a robust manner and for the optimal region of parameter space to be trivially identified. The effectiveness of the approach is illustrated by using the method to refine the chlorine 6-12 Lennard-Jones parameters against experimental solvation free enthalpies in water and hexane as well as the density and heat of vaporization of the liquid at atmospheric pressure for a set of 10 aromatic-chloro compounds simultaneously. Single-step perturbation is used to efficiently calculate solvation free enthalpies for a wide range of parameter combinations. The capacity of this approach to parametrize accurate and transferrable force fields is discussed.
提出了一种对原子相互作用函数进行参数化的通用方法。该方法基于对与计算数据和目标数据之间的差异相对应的表面进行分析，此差异是参数替代组合（参数空间映射）的函数。与局部值或梯度相反，对参数空间中的表面进行考虑能够更好地理解正在优化的参数与给定目标数据集之间的关系。这进而能够以稳健的方式组合来自多个分子的一系列目标数据，并能轻松识别参数空间的最佳区域。通过使用该方法针对水中和己烷中的实验溶剂化自由焓以及一组10种芳族氯化合物在大气压下的液体密度和汽化热来优化氯的6 - 12 Lennard - Jones参数，说明了该方法的有效性。单步微扰用于有效计算各种参数组合的溶剂化自由焓。讨论了这种方法对准确且可转移的力场进行参数化的能力。
