Assessment of standard force field models against high-quality ab initio potential curves for prototypes of pi-pi, CH/pi, and SH/pi interactions.
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.
Sherrill
C David
CD
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA. sherrill@gatech.edu
Sumpter
Bobby G
BG
Sinnokrot
Mutasem O
MO
Marshall
Michael S
MS
Hohenstein
Edward G
EG
Walker
Ross C
RC
Gould
Ian R
IR
D003198:Computer Simulation; D008956:Models, Chemical; D011789:Quantum Theory