Beyond Kohn-Sham Approximation: Hybrid Multistate Wave Function and Density Functional Theory

Jiali Gao, Adam Grofe, Haisheng Ren, Peng Bao

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)5143-5149
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume7
Issue number24
DOIs
StatePublished - Dec 15 2016

Bibliographical note

Funding Information:
This work has been supported in part by the National Natural Science Foundation of China (Number 21533003) and the National Institutes of Health (GM46736).

Publisher Copyright:
© 2016 American Chemical Society.

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