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

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journal contribution
posted on 26.01.2016, 17:49 by Chad E. Hoyer, Soumen Ghosh, Donald G. Truhlar, Laura Gagliardi
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.