Assessment of standard force field models against high‐quality ab initio potential curves for prototypes of π–π, CH/π, and SH/π interactions |
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| Authors: | C. David Sherrill Bobby G. Sumpter Mutasem O. Sinnokrot Michael S. Marshall Edward G. Hohenstein Ross C. Walker Ian R. Gould |
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| Affiliation: | 1. Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332‐0400;2. Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831;3. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831;4. Department of Chemistry, Faculty of Science, University of Jordan, Amman 11942, Jordan;5. San Diego Supercomputer Center, University of California San Diego, La Jolla, California 92093‐0505;6. Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom |
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| 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 |
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| Keywords: | quantum chemistry electronic structure coupled cluster theory molecular mechanics computational chemistry |
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