title: Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.
abstract: The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Soumen
authors.initials: S
authors.lastname: Ghosh
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Andrew L
authors.initials: AL
authors.lastname: Sonnenberger
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Chad E
authors.initials: CE
authors.lastname: Hoyer
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Donald G
authors.initials: DG
authors.lastname: Truhlar
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
mesh_terms: D005030:Ethylenes / Q000737:chemistry; D005466:Fluorocarbons / Q000737:chemistry; D008956:Models, Chemical; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D005030:Ethylenes; D005466:Fluorocarbons; C036216:ethylene; C015531:tetrafluoroethylene