Localized Active Space Pair-Density Functional Theory

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

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


Accurate quantum chemical methods for the prediction of spin-state energy gaps for strongly correlated systems are computationally expensive and scale poorly with the size of the system. This makes calculations for many experimentally interesting molecules impractical even with abundant computational resources. Previous work has shown that the localized active space (LAS) self-consistent field (SCF) method can be an efficient way to obtain multiconfiguration SCF wave functions of comparable quality to the corresponding complete active space (CAS) ones. To obtain quantitative results, a post-SCF method is needed to estimate the complete correlation energy. One such method is multiconfiguration pair-density functional theory (PDFT), which calculates the energy based on the density and on-top pair density obtained from a multiconfiguration wave function. In this work, we introduce localized-active-space PDFT, which uses a LAS wave function for subsequent PDFT calculations. The method is tested by computing spin-state energies and gaps in conjugated organic molecules and a bimetallic compound and comparing to the corresponding CAS-PDFT values.

Original languageEnglish (US)
Pages (from-to)2843-2851
Number of pages9
JournalJournal of Chemical Theory and Computation
Issue number5
StatePublished - May 11 2021

Bibliographical note

Funding Information:
This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences under Award DE-FG02-17ER16362.

Publisher Copyright:
© 2021 American Chemical Society.

PubMed: MeSH publication types

  • Journal Article


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