Assessment of standard force field models against high-quality ab initio potential curves for prototypes of π–π, CH/π, and SH/π interactions†

  1. C. David Sherrill1,*,
  2. Bobby G. Sumpter2,3,
  3. Mutasem O. Sinnokrot4,
  4. Michael S. Marshall1,
  5. Edward G. Hohenstein1,
  6. Ross C. Walker5,
  7. Ian R. Gould6

Article first published online: 25 FEB 2009

DOI: 10.1002/jcc.21226

Issue

Journal of Computational Chemistry

Journal of Computational Chemistry

Volume 30, Issue 14, pages 2187–2193, 15 November 2009

Additional Information

How to Cite

Sherrill, C. D., Sumpter, B. G., Sinnokrot, M. O., Marshall, M. S., Hohenstein, E. G., Walker, R. C. and Gould, I. R. (2009), Assessment of standard force field models against high-quality ab initio potential curves for prototypes of π–π, CH/π, and SH/π interactions. Journal of Computational Chemistry, 30: 2187–2193. doi: 10.1002/jcc.21226

Author Information

  1. 1

    Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400

  2. 2

    Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831

  3. 3

    Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831

  4. 4

    Department of Chemistry, Faculty of Science, University of Jordan, Amman 11942, Jordan

  5. 5

    San Diego Supercomputer Center, University of California San Diego, La Jolla, California 92093-0505

  6. 6

    Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom

*Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400

  1. †

    This work is dedicated in memory of Tamer Sinnokrot.

Publication History

  1. Issue published online: 24 AUG 2009
  2. Article first published online: 25 FEB 2009
  3. Manuscript Accepted: 31 DEC 2008
  4. Manuscript Revised: 19 DEC 2008
  5. Manuscript Received: 9 AUG 2008

Funded by

  • National Science Foundation. Grant Number: CHE-0715268
  • CRIF. Grant Number: CHE-04-43564
  • Petroleum Research Fund of the ACS. Grant Number: 44262-AC6
  • Division of Scientific User Facilities, U.S. Department of Energy
  • SDSC Strategic Applications Collaborations program and National Science Foundation. Grant Number: 0438741

SEARCH

SEARCH BY CITATION

ARTICLE TOOLS

View Full Article (HTML) Get PDF (639K)

Keywords:

  • quantum chemistry;
  • electronic structure;
  • coupled cluster theory;
  • molecular mechanics;
  • computational chemistry

Graphical Abstract

Thumbnail image of graphical abstract

Abstract

Several popular force fields, namely, CHARMM, AMBER, OPLS-AA, and MM3, have been tested for their ability to reproduce highly accurate quantum mechanical potential energy curves for noncovalent interactions in the benzene dimer, the benzene-CH4 complex, and the benzene-H2S complex. All of the force fields are semi-quantitatively correct, but none of them is consistently reliable quantitatively. Re-optimization of Lennard-Jones parameters and symmetry-adapted perturbation theory analysis for the benzene dimer suggests that better agreement cannot be expected unless more flexible functional forms (particularly for the electrostatic contributions) are employed for the empirical force fields. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009

View Full Article (HTML) Get PDF (639K)