title: Exchange-Correlation Effects for Noncovalent Interactions in Density Functional Theory.
abstract: In this article, we develop an understanding of how errors from exchange-correlation functionals affect the modeling of noncovalent interactions in dispersion-corrected density-functional theory. Computed CCSD(T) reference binding energies for a collection of small-molecule clusters are decomposed via a molecular many-body expansion and are used to benchmark density-functional approximations, including the effect of semilocal approximation, exact-exchange admixture, and range separation. Three sources of error are identified. Repulsion error arises from the choice of semilocal functional approximation. This error affects intermolecular repulsions and is present in all n-body exchange-repulsion energies with a sign that alternates with the order n of the interaction. Delocalization error is independent of the choice of semilocal functional but does depend on the exact exchange fraction. Delocalization error misrepresents the induction energies, leading to overbinding in all induction n-body terms, and underestimates the electrostatic contribution to the 2-body energies. Deformation error affects only monomer relaxation (deformation) energies and behaves similarly to bond-dissociation energy errors. Delocalization and deformation errors affect systems with significant intermolecular orbital interactions (e.g., hydrogen- and halogen-bonded systems), whereas repulsion error is ubiquitous. Many-body errors from the underlying exchange-correlation functional greatly exceed in general the magnitude of the many-body dispersion energy term. A functional built to accurately model noncovalent interactions must contain a dispersion correction, semilocal exchange, and correlation components that minimize the repulsion error independently and must also incorporate exact exchange in such a way that delocalization error is absent.
authors.affiliation: National Institute for Nanotechnology, National Research Council of Canada , 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9, Canada.|Department of Chemistry, University of British Columbia , Okanagan, 3247 University Way, Kelowna, British Columbia V1V 1V7, Canada.
authors.forename: A
authors.initials: A
authors.lastname: Otero-de-la-Roza
authors.affiliation: National Institute for Nanotechnology, National Research Council of Canada , 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9, Canada.|Department of Chemistry, University of British Columbia , Okanagan, 3247 University Way, Kelowna, British Columbia V1V 1V7, Canada.
authors.forename: Gino A
authors.initials: GA
authors.lastname: DiLabio
authors.affiliation: Department of Chemistry, Dalhousie University , 6274 Coburg Road, Halifax, Nova Scotia B3H 4R2, Canada.
authors.forename: Erin R
authors.initials: ER
authors.lastname: Johnson