Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer

Soumen Ghosh, Andrew L. Sonnenberger, Chad E. Hoyer, Donald G. Truhlar, Laura Gagliardi

Research output: Contribution to journalArticlepeer-review

33 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)3643-3649
Number of pages7
JournalJournal of Chemical Theory and Computation
Volume11
Issue number8
DOIs
StatePublished - Aug 11 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

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