DOI: 10.1002/jcc.22996. Atomic multipoles: Electrostatic potential fit, local reference axis systems, and conformational dependence

Atomic multipoles: Electrostatic potential fit, local reference axis systems, and conformational dependence

10.1002/jcc.22996

Crossref journal-article

Wiley

Journal of Computational Chemistry (311)

Abstract

AbstractCurrently, all standard force fields for biomolecular simulations use point charges to model intermolecular electrostatic interactions. This is a fast and simple approach but has deficiencies when the electrostatic potential (ESP) is compared to that from ab initio methods. Here, we show how atomic multipoles can be rigorously implemented into common biomolecular force fields. For this, a comprehensive set of local reference axis systems is introduced, which represents a universal solution for treating atom‐centered multipoles for all small organic molecules and proteins. Furthermore, we introduce a new method for fitting atomic multipole moments to the quantum mechanically derived ESP. This methods yields a 50–90% error reduction compared to both point charges fit to the ESP and multipoles directly calculated from the ab initio electron density. It is shown that it is necessary to directly fit the multipole moments of conformational ensembles to the ESP. Ignoring the conformational dependence or averaging over parameters from different conformations dramatically deteriorates the results obtained with atomic multipole moments, rendering multipoles worse than partial charges. © 2012 Wiley Periodicals, Inc.

Bibliography

Kramer, C., Gedeck, P., & Meuwly, M. (2012). Atomic multipoles: Electrostatic potential fit, local reference axis systems, and conformational dependence. Journal of Computational Chemistry, 33(20), 1673â1688. Portico.

Authors 3

Christian Kramer (first)
Peter Gedeck (additional)
Markus Meuwly (additional)

References 48 Referenced 62

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Dates

Type	When
Created	13 years, 3 months ago (April 28, 2012, 7:39 a.m.)
Deposited	1 year, 10 months ago (Oct. 10, 2023, 6:16 a.m.)
Indexed	2 weeks, 3 days ago (Aug. 6, 2025, 8:23 a.m.)
Issued	13 years, 3 months ago (April 28, 2012)
Published	13 years, 3 months ago (April 28, 2012)
Published Online	13 years, 3 months ago (April 28, 2012)
Published Print	13 years ago (July 30, 2012)

Funders 0

None

BibTeX

@article{Kramer_2012, title={Atomic multipoles: Electrostatic potential fit, local reference axis systems, and conformational dependence}, volume={33}, ISSN={1096-987X}, url={http://dx.doi.org/10.1002/jcc.22996}, DOI={10.1002/jcc.22996}, number={20}, journal={Journal of Computational Chemistry}, publisher={Wiley}, author={Kramer, Christian and Gedeck, Peter and Meuwly, Markus}, year={2012}, month=apr, pages={1673–1688} }

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