Simultaneous parametrization of torsional and third‐neighbor interaction terms in force‐field development: The LLS‐SC algorithm

The calibration of torsional interaction terms by fitting relative gas‐phase conformational energies against their quantum‐mechanical values is a common procedure in force‐field development. However, much less attention has been paid to the optimization of third‐neighbor nonbonded interaction parame...

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Veröffentlicht in:Journal of computational chemistry 2022-04, Vol.43 (9), p.644-653
Hauptverfasser: Gonçalves, Yan M. H., Kashefolgheta, Sadra, Oliveira, Marina P., Hünenberger, Philippe H., Horta, Bruno A. C.
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Sprache:eng
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Zusammenfassung:The calibration of torsional interaction terms by fitting relative gas‐phase conformational energies against their quantum‐mechanical values is a common procedure in force‐field development. However, much less attention has been paid to the optimization of third‐neighbor nonbonded interaction parameters, despite their strong coupling with the torsions. This article introduces an algorithm termed LLS‐SC, aimed at simultaneously parametrizing torsional and third‐neighbor interaction terms based on relative conformational energies. It relies on a self‐consistent (SC) procedure where each iteration involves a linear least‐squares (LLS) regression followed by a geometry optimization of the reference structures. As a proof‐of‐principle, this method is applied to obtain torsional and third‐neighbor interaction parameters for aliphatic chains in the context of the GROMOS 53A6 united‐atom force field. The optimized parameter set is compared to the original one, which has been fitted manually against thermodynamic properties for small linear alkanes. The LLS‐SC implementation is freely available under http://github.com/mssm-labmmol/profiler. When using classical force fields, the conformational properties of (bio)molecular systems are strongly dependent on the torsional and third‐neighbor interaction terms of the potential‐energy function. Here, we propose a method to optimize simultaneously the torsional and third‐neighbor interaction parameters, based on fitting against reference relative conformational energies of representative molecules. The method consists on a self‐consistent procedure where each iteration involves a linear least‐squares regression followed by a geometry optimization of the reference structures.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.26819