☆ 4.8 Article

A New Mixing of Nonlocal Exchange and Nonlocal Correlation with Multiconfiguration Pair-Density Functional Theory

JOURNAL OF PHYSICAL CHEMISTRY LETTERS (2020)

期刊

JOURNAL OF PHYSICAL CHEMISTRY LETTERS

卷 11, 期 23, 页码 10158-10163

出版社

AMER CHEMICAL SOC

DOI: 10.1021/acs.jpclett.0c02956

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Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Physics, Atomic, Molecular & Chemical

资金

Air Force Office of Scientific Research [FA9550-16-1-0134]

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Reagent

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We propose a hybrid multiconfiguration pair-density functional theory (HMC-PDFT) that is a weighted average of complete-active-space self-consistent-field (CASSCF) and multiconfiguration pair-density functional theory (MC-PDFT) energies with a semiempirical parameter to control the fraction of CASSCF energy. We also explore a more general two-parameter hybrid method with a scaled correlation energy that allows us to compare to the recently proposed lambda-MC-PDFT method. We scan the parameter space for the scaled-correlation method using test sets consisting of electronic excitation energies and diatomic bond energies, and we find no significant improvement by introducing the scaling parameter. We find that unscaled HMC-PDFT offers significantly improved accuracy over both CASSCF and the original MC-PDFT for a wide range of systems, and we present as an example of this approach tPBEO, the translated MC-PDFT generalization of the popular PBEO hybrid Kohn-Sham density functional.

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