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

作者：Hoyer Chad E; Ghosh Soumen; Truhlar Donald G; Gagliardi Laura

来源：Journal of Physical Chemistry Letters, 2016, 7(3): 586-591.

DOI：10.1021/acs.jpclett.5b02773

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.

• 出版日期2016-2-4