Ayers, Paul W

Van Speybroeck, Veronique

Verstraelen, Toon

Waroquier, Michel

English

Verstraelen, ToonWE050019983841958010017750560000-0001-9288-5608F6DA9612-F0ED-11E1-A9DE-61C894A0A6B4

Van Speybroeck, VeroniqueTW17WE058010011535490000-0003-2206-178XF542886E-F0ED-11E1-A9DE-61C894A0A6B4

Waroquier, MichelWE05801000350166F3D4D9E6-F0ED-11E1-A9DE-61C894A0A6B4

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Extended Hirshfeld: atomic charges that combine accurate electrostatics with transferability

Ghent University Academic Bibliography

 COMP Emilio Esposito, Scott Wildman Tuesday, March 18, 2014 294 - Extended Hirshfeld: Atomic charges that combine accurate electrostatics with transferabilityToon Verstraelen1, Toon.Verstraelen@UGent.be, Paul W Ayers2, Veronique Van Speybroeck1, Michel Waroquier1. (1) Centerfor Molecular Modeling, Ghent University, Zwijnaarde, Oost-Vlaanderen B9052, Belgium, (2) Department of Chemistry, McMasterUniversity, Hamilton, Ontario L8S 4M1, CanadaNon-polarizable force fields usually model the molecular electrostatics as the interaction between a set of atomic partial charges.A myriad of population analysis schemes can be found in the literature to derive atomic charges from a wavefunction computedwith an electronic structure method. Such methods are convenient tools to parameterize the electrostatic energy term in a force-field model. For the development of a force field, the atomic charges must satisfy two criteria: (i) the charges should accuratelydescribe the electrostatic interactions and (ii) the charges must be transferable from (small) model systems to the actualapplication of interest. Each charge definition makes a specific compromise between these two criteria. For example, ESP fittedcharges obviously reproduce the ESP very well but are heavily geometry and environment dependent. The opposite behavior isfound with QTAIM charges, which are very transferable but typically overestimate the electrostatic interactions. (For QTAIM, onemust include higher atomic multipoles to converge the ESP.) We recently proposed the Extended Hirshfeld scheme with animproved trade-off between both criteria. New benchmarks reveal that Extended Hirshfeld also works well for intra-molecularelectrostatic interactions, outperforming ESP fitted charges, which are easily over-fitted to reproduce the ESP outside themolecular van der Waals surface.Tuesday, March 18, 2014 06:00 PMPoster Session (06:00 PM - 08:00 PM)Location: OmniDallas HotelRoom: Dallas Ballroom D/H *ACS does not own copyrights to the individual abstracts. For permission, please contact the author(s) of the abstract. Close Window

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Extended Hirshfeld: atomic charges that combine accurate electrostatics with transferability

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Ghent University Academic Bibliography