title: Comparison of the performance of exact-exchange-based density functional methods.
abstract: How to describe nondynamic electron correlation is still a major challenge to density functional theory (DFT). Recent models designed particularly for this problem, such as Becke'05 (B05) and Perdew-Staroverov-Tao-Scuseria (PSTS) functionals employ the exact-exchange density, the efficient calculation of which is technically quite challenging. We have recently implemented self-consistently the B05 functional based on an efficient resolution-identity (RI) technique. In this study, we report a self-consistent RI implementation of the PSTS functional. In contrast to its original implementation, our version brings no limitation on the choice of the basis set. We have also implemented the Mori-Sanchez-Cohen-Yang-2 (MCY2) functional, another recent DFT method that includes full exact exchange. The performance of PSTS, B05, and MCY2 is validated on thermochemistry, reaction barriers, and dissociation energy curves, with an emphasis on nondynamic correlation effects in the discussion. All three methods perform rather well in general, B05 and MCY2 being on average somewhat better than PSTS. We include also results with other functionals that represent various aspects of the development in this field in recent years, including B3LYP, M06-HF, M06-2X, ωB97X, and TPSSh. The performance of the heavy-parameterized functionals M06-2X and ωB97X is on average better than that of B05, MCY2, and PSTS for standard thermodynamic properties and reactions, while the latter functionals do better in hydrogen abstraction reactions and dissociation processes. In particular, B05 is found to be the only functional that yields qualitatively correct dissociation curves for two-center symmetric radicals like He(2)(+). Finally, we compare the performance of all these functionals on a strongly correlated exemplary case system, the NO dimer. Only PSTS, B05, and MCY2 describe the system qualitatively correctly. Overall, this new type of functionals show good promise of overcoming some of the difficulties DFT encounters for systems with strong nondynamic correlation.
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.
authors.forename: Fenglai
authors.initials: F
authors.lastname: Liu
authors.forename: Emil
authors.initials: E
authors.lastname: Proynov
authors.forename: Jian-Guo
authors.initials: JG
authors.lastname: Yu
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Furlani
authors.forename: Jing
authors.initials: J
authors.lastname: Kong
mesh_terms: D019281:Dimerization; D005459:Fluorides / Q000737:chemistry; D006371:Helium / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D009569:Nitric Oxide / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D006371:Helium; D009569:Nitric Oxide; D006859:Hydrogen; D009584:Nitrogen; D005459:Fluorides