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

Riddhish Pandharkar, Matthew R. Hermes, Donald G. Truhlar, Laura Gagliardi

Research output: Contribution to journalArticlepeer-review

Abstract

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 λ-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 "tPBE0", the "translated"MC-PDFT generalization of the popular PBE0 hybrid Kohn-Sham density functional.

Original languageEnglish (US)
Pages (from-to)10158-10163
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume11
Issue number23
DOIs
StatePublished - Dec 3 2020

Bibliographical note

Funding Information:
This work was supported by the Air Force Office of Scientific Research (Grant FA9550-16-1-0134).

PubMed: MeSH publication types

  • Journal Article

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