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The significance of parameters in charge equilibration models

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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
Charge equilibration models such as the electronegativity equalization method (EEM) and the split charge equilibration (SQE) are extensively used in the literature for the efficient computation of accurate atomic charges in molecules. However, there is no consensus on a generic set of optimal parameters, even when one only considers parameters calibrated against atomic charges in organic molecules. In this work, the origin of the disagreement in the parameters is investigated by comparing and analyzing six sets of parameters based on two sets of molecules and three calibration procedures. The resulting statistical analysis clearly indicates that the conventional least-squares cost function based solely on atomic charges is in general ill-conditioned and not capable of fixing all parameters in a charge-equilibration model. Methodological guidelines are formulated to improve the stability of the parameters. Although in this case a simple interpretation of individual parameters is not possible, charge equilibration models remain of great practical use for the computation of atomic charges.
Keywords
ATOMIC CHARGES, FORCE-FIELD, ELECTRONEGATIVITY EQUALIZATION METHOD, MOLECULAR-DYNAMICS, HARDNESS MATRIX, FUKUI FUNCTIONS, SIMULATIONS, MACROMOLECULES, VALIDATION, SOLVATION

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Chicago
Verstraelen, Toon, Patrick Bultinck, Veronique Van Speybroeck, PW Ayers, Dimitri Van Neck, and Michel Waroquier. 2011. “The Significance of Parameters in Charge Equilibration Models.” Journal of Chemical Theory and Computation 7 (6): 1750–1764.
APA
Verstraelen, T., Bultinck, P., Van Speybroeck, V., Ayers, P., Van Neck, D., & Waroquier, M. (2011). The significance of parameters in charge equilibration models. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 7(6), 1750–1764.
Vancouver
1.
Verstraelen T, Bultinck P, Van Speybroeck V, Ayers P, Van Neck D, Waroquier M. The significance of parameters in charge equilibration models. JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 2011;7(6):1750–64.
MLA
Verstraelen, Toon, Patrick Bultinck, Veronique Van Speybroeck, et al. “The Significance of Parameters in Charge Equilibration Models.” JOURNAL OF CHEMICAL THEORY AND COMPUTATION 7.6 (2011): 1750–1764. Print.
@article{1339213,
  abstract     = {Charge equilibration models such as the electronegativity equalization method (EEM) and the split charge equilibration (SQE) are extensively used in the literature for the efficient computation of accurate atomic charges in molecules. However, there is no consensus on a generic set of optimal parameters, even when one only considers parameters calibrated against atomic charges in organic molecules. In this work, the origin of the disagreement in the parameters is investigated by comparing and analyzing six sets of parameters based on two sets of molecules and three calibration procedures. The resulting statistical analysis clearly indicates that the conventional least-squares cost function based solely on atomic charges is in general ill-conditioned and not capable of fixing all parameters in a charge-equilibration model. Methodological guidelines are formulated to improve the stability of the parameters. Although in this case a simple interpretation of individual parameters is not possible, charge equilibration models remain of great practical use for the computation of atomic charges.},
  author       = {Verstraelen, Toon and Bultinck, Patrick and Van Speybroeck, Veronique and Ayers, PW and Van Neck, Dimitri and Waroquier, Michel},
  issn         = {1549-9618},
  journal      = {JOURNAL OF CHEMICAL THEORY AND COMPUTATION},
  keyword      = {ATOMIC CHARGES,FORCE-FIELD,ELECTRONEGATIVITY EQUALIZATION METHOD,MOLECULAR-DYNAMICS,HARDNESS MATRIX,FUKUI FUNCTIONS,SIMULATIONS,MACROMOLECULES,VALIDATION,SOLVATION},
  language     = {eng},
  number       = {6},
  pages        = {1750--1764},
  title        = {The significance of parameters in charge equilibration models},
  url          = {http://dx.doi.org/10.1021/ct200006e},
  volume       = {7},
  year         = {2011},
}

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