title: Beyond Kohn-Sham Approximation: Hybrid Multistate Wave Function and Density Functional Theory.
abstract: A multistate density functional theory (MSDFT) is presented in which the energies and densities for the ground and excited states are treated on the same footing using multiconfigurational approaches. The method can be applied to systems with strong correlation and to correctly describe the dimensionality of the conical intersections between strongly coupled dissociative potential energy surfaces. A dynamic-then-static framework for treating electron correlation is developed to first incorporate dynamic correlation into contracted state functions through block-localized Kohn-Sham density functional theory (KSDFT), followed by diagonalization of the effective Hamiltonian to include static correlation. MSDFT can be regarded as a hybrid of wave function and density functional theory. The method is built on and makes use of the current approximate density functional developed in KSDFT, yet it retains its computational efficiency to treat strongly correlated systems that are problematic for KSDFT but too large for accurate WFT. The results presented in this work show that MSDFT can be applied to photochemical processes involving conical intersections.
authors.affiliation: Theoretical Chemistry Institute, Jilin University , Changchun 130023, P. R. China.|Department of Chemistry and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Jiali
authors.identifier: http://orcid.org/0000-0003-0106-7154
authors.initials: J
authors.lastname: Gao
authors.affiliation: Theoretical Chemistry Institute, Jilin University , Changchun 130023, P. R. China.|Department of Chemistry and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Adam
authors.initials: A
authors.lastname: Grofe
authors.affiliation: Department of Chemistry and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Haisheng
authors.initials: H
authors.lastname: Ren
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.
authors.forename: Peng
authors.initials: P
authors.lastname: Bao