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Assessment of standard force field models against high‐quality ab initio potential curves for prototypes of π–π, CH/π, and SH/π interactions
Author(s) -
Sherrill C. David,
Sumpter Bobby G.,
Sinnokrot Mutasem O.,
Marshall Michael S.,
Hohenstein Edward G.,
Walker Ross C.,
Gould Ian R.
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21226
Subject(s) - force field (fiction) , benzene , ab initio , dimer , computational chemistry , potential energy , chemistry , perturbation theory (quantum mechanics) , chemical physics , molecular physics , quantum mechanics , physics , organic chemistry
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‐CH 4 complex, and the benzene‐H 2 S 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