Modeling pi-pi interactions with the effective fragment potential method: the benzene dimer and substituents.
This study compares the results of the general effective fragment potential (EFP2) method to the results of a previous combined coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] and symmetry-adapted perturbation theory (SAPT) study [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690] on substituent effects in pi-pi interactions. EFP2 is found to accurately model the binding energies of the benzene-benzene, benzene-phenol, benzene-toluene, benzene-fluorobenzene, and benzene-benzonitrile dimers, as compared with high-level methods [Sinnokrot and Sherrill, J. Am. Chem. Soc., 2004, 126, 7690], but at a fraction of the computational cost of CCSD(T). In addition, an EFP-based Monte Carlo/simulated annealing study was undertaken to examine the potential energy surface of the substituted dimers.
Smith
Toni
T
Department of Chemistry and Ames Laboratory-USDOE, Iowa State University, Ames, Iowa 50011, USA.
Slipchenko
Lyudmila V
LV
Gordon
Mark S
MS
D001554:Benzene / Q000737:chemistry*; D019281:Dimerization; D008958:Models, Molecular; D008968:Molecular Conformation; D013816:Thermodynamics
D001554:Benzene