Density matrix renormalization group pair-density functional theory (DMRG-PDFT)

Singlet-triplet gaps in polyacenes and polyacetylenes

Prachi Sharma, Varinia Bernales, Stefan Knecht, Donald G Truhlar, Laura Gagliardi

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The density matrix renormalization group (DMRG) is a powerful method to treat static correlation. Here we present an inexpensive way to calculate correlation energy starting from a DMRG wave function using pair-density functional theory (PDFT). We applied this new approach, called DMRG-PDFT, to study singlet-triplet gaps in polyacenes and polyacetylenes that require active spaces larger than the feasibility limit of the conventional complete active-space self-consistent field (CASSCF) method. The results match reasonably well with the most reliable literature values and have only a moderate dependence on the compression of the initial DMRG wave function. Furthermore, DMRG-PDFT is significantly less expensive than other commonly applied ways of adding additional correlation to DMRG, such as DMRG followed by multireference perturbation theory or multireference configuration interaction.

Original languageEnglish (US)
Pages (from-to)1716-1723
Number of pages8
JournalChemical Science
Volume10
Issue number6
DOIs
StatePublished - Jan 1 2019

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Polyacetylenes
Aromatic polymers
Density functional theory
Wave functions

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Density matrix renormalization group pair-density functional theory (DMRG-PDFT) : Singlet-triplet gaps in polyacenes and polyacetylenes. / Sharma, Prachi; Bernales, Varinia; Knecht, Stefan; Truhlar, Donald G; Gagliardi, Laura.

In: Chemical Science, Vol. 10, No. 6, 01.01.2019, p. 1716-1723.

Research output: Contribution to journalArticle

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