Hoyer Chad E, Ghosh Soumen, Truhlar Donald G, Gagliardi Laura
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States.
J Phys Chem Lett. 2016 Feb 4;7(3):586-91. doi: 10.1021/acs.jpclett.5b02773. Epub 2016 Jan 26.
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.
对电子激发态的正确描述对于解释化学系统中的可见-紫外光谱、光化学反应和激发态电荷转移过程至关重要。我们最近提出了一种称为多组态对密度泛函理论（MC-PDFT）的理论，它基于多组态波函数理论和一种新型密度泛函（称为顶密度泛函）的结合。在此，我们表明，对于包含价态、里德堡态和电荷转移激发的有机化学数据库，采用第一代顶密度泛函的MC-PDFT与CASPT2的表现相当。这些结果对于实际应用非常令人鼓舞。
