Publisher： John Wiley & Sons Inc
E-ISSN： 1096-987x|36|14|1083-1101
ISSN： 0192-8651
Source： JOURNAL OF COMPUTATIONAL CHEMISTRY, Vol.36, Iss.14, 2015-05, pp. : 1083-1101
Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.
Abstract
Automated methods for force field parametrization have attracted renewed interest of the community, but the robustness issues associated with the often ill‐conditioned nature of parameter optimization have been vastly underappreciated in the recent literature. For this reason, this article offers a detailed description of the origin and nature of these issues. This includes a discussion of the restrained electrostatic potential fit (RESP) charge model, which does contain explicit robustness‐enhancing measures albeit not in the context of bonded parameters, and which forms an inspiration for the present work. It is also discussed how all the bonded parameters in a Class I force field can be simultaneously fit using the linear least squares (LLS) procedure, and a novel restraining strategy is presented that overcomes robustness issues in the LLS fitting of bonded parameters while minimally impacting the fitted values of well‐behaved parameters. Two variants of this methodology are then validated through a number of case studies, including the fitting of bond‐charge increments, which illustrates the method's potential for robustly solving general LLS problems beyond force field parametrization. © 2015 Wiley Periodicals, Inc.
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