title: Evaluation of the performance of post-Hartree-Fock methods in terms of intermolecular distance in noncovalent complexes.
abstract: Dissociation curves calculated using multiple correlated QM methods for 66 noncovalent complexes (Řezáč et al., J Chem Theory Comput 2011, 7, 2427) have allowed us to interpolate equilibrium intermolecular distances for each studied method. Comparison of these data with CCSD(T)/complete basis set reference geometries provides information on how these methods perform in geometry optimizations. The large set of systems considered here is necessary for reliable statistical evaluation of the results and assessment of the robustness of the studied methods. Our results show that advanced methods such as MP3 and CCSD provide significant improvement over MP2 only when empirical scaling is used. The best results can be achieved with spin component scaled CCSD optimized for noncovalent interactions, with a root mean square error of 0.4% of the equilibrium distance. Scaled MP3, the MP2.5 method, yields comparably good results (error 0.5%) while being substantially cheaper.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems, 166 10 Prague, Czech Republic. rezac@uochb.cas.cz
authors.forename: Jan
authors.initials: J
authors.lastname: Rezáč
authors.forename: Kevin E
authors.initials: KE
authors.lastname: Riley
authors.forename: Pavel
authors.initials: P
authors.lastname: Hobza
mesh_terms: D056831:Coordination Complexes; D006860:Hydrogen Bonding; D008956:Models, Chemical
chemical_list: D056831:Coordination Complexes