Active Space Dependence in Multiconfiguration Pair-Density Functional Theory

Research output: Contribution to journalArticle

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Abstract

In multiconfiguration pair-density functional theory (MC-PDFT), multiconfiguration self-consistent-field calculations and on-top density functionals are combined to describe both static and dynamic correlation. Here, we investigate how the MC-PDFT total energy and its components depend on the active space choice in the case of the H2 and N2 molecules. The active space dependence of the on-top pair density, the total density, the ratio of on-top pair density to half the square of the electron density, and the satisfaction of the virial theorem are also explored. We find that the density and on-top pair density do not change significantly with changes in the active space. However, the on-top ratio does change significantly with respect to active space change, and this affects the on-top energy. This study provides a foundation for designing on-top density functionals and automatizing the active space choice in MC-PDFT.

Original languageEnglish (US)
Pages (from-to)660-669
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume14
Issue number2
DOIs
StatePublished - Feb 13 2018

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Density functional theory
density functional theory
Carrier concentration
functionals
Molecules
virial theorem
self consistent fields
energy
molecules

PubMed: MeSH publication types

  • Journal Article

Cite this

Active Space Dependence in Multiconfiguration Pair-Density Functional Theory. / Sharma, Prachi; Truhlar, Donald G.; Gagliardi, Laura.

In: Journal of Chemical Theory and Computation, Vol. 14, No. 2, 13.02.2018, p. 660-669.

Research output: Contribution to journalArticle

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