title: Modeling pi-pi interactions with the effective fragment potential method: the benzene dimer and substituents.
abstract: 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.
authors.affiliation: Department of Chemistry and Ames Laboratory-USDOE, Iowa State University, Ames, Iowa 50011, USA.
authors.forename: Toni
authors.initials: T
authors.lastname: Smith
authors.forename: Lyudmila V
authors.initials: LV
authors.lastname: Slipchenko
authors.forename: Mark S
authors.initials: MS
authors.lastname: Gordon
mesh_terms: D001554:Benzene / Q000737:chemistry*; D019281:Dimerization; D008958:Models, Molecular; D008968:Molecular Conformation; D013816:Thermodynamics
chemical_list: D001554:Benzene