Scaling exchange and correlation in the on-top density functional of multiconfiguration pair-density functional theory: effect on electronic excitation energies and bond energies

Davide Presti, Jan Kadlec, Donald G. Truhlar, Laura Gagliardi

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Multiconfiguration pair-density functional (MC-PDFT) theory provides an economical way to calculate the ground-state and excited-state energetics of strongly correlated systems. The energy is calculated from the kinetic energy, density, and on-top pair-density of a multiconfiguration wave function as the sum of kinetic energy, classical Coulomb energy, and on-top density functional energy. We have usually found good results with the translated Perdew–Burke–Ernzerhof (tPBE) on-top density functional, and in this article, we examine whether the results can be systematically improved by introducing scaling constants into the exchange and correlation terms. We find that only a small improvement is possible for electronic excitation energies and that no improvement is possible for bond energies.

Original languageEnglish (US)
Article number30
JournalTheoretical Chemistry Accounts
Volume139
Issue number2
DOIs
StatePublished - Feb 1 2020

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation under grant CHE–1746186.

Funding Information:
This work was supported by the National Science Foundation under grant CHE?1746186.

Publisher Copyright:
© 2020, Springer-Verlag GmbH Germany, part of Springer Nature.

Keywords

  • Benchmark
  • Bond energies
  • Excitation energies
  • MC-PDFT
  • On-top pair-density functionals
  • Pair-density

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