Multiconfiguration Pair-Density Functional Theory Is as Accurate as CASPT2 for Electronic Excitation

A correct description of electronically excited states is critical to the interpretation of visible–ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. We have recently proposed a theory called multiconfiguration pair-density functional theo...

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Published inThe journal of physical chemistry letters Vol. 7; no. 3; pp. 586 - 591
Main Authors Hoyer, Chad E, Ghosh, Soumen, Truhlar, Donald G, Gagliardi, Laura
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 04.02.2016
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Summary:A correct description of electronically excited states is critical to the interpretation of visible–ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. 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 and a new kind of density functional called an on-top density functional. Here, we show that MC-PDFT with a first-generation on-top density functional performs as well as CASPT2 for an organic chemistry database including valence, Rydberg, and charge-transfer excitations. The results are very encouraging for practical applications.
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ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.5b02773