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Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet-triplet gaps in polyacenes and polyacetylenes.
Journal article

Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet-triplet gaps in polyacenes and polyacetylenes.

  • Sharma P Department of Chemistry , Chemical Theory Center , Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455 , USA . Email: truhlar@umn.edu ; Email: gagliard@umn.edu.
  • Bernales V Department of Chemistry , Chemical Theory Center , Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455 , USA . Email: truhlar@umn.edu ; Email: gagliard@umn.edu.
  • Knecht S Laboratory of Physical Chemistry , ETH Zürich , Vladimir-Prelog-Weg 2 , CH-8093 Zürich , Switzerland . Email: stefan.knecht@phys.chem.ethz.ch.
  • Truhlar DG Department of Chemistry , Chemical Theory Center , Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455 , USA . Email: truhlar@umn.edu ; Email: gagliard@umn.edu.
  • Gagliardi L Department of Chemistry , Chemical Theory Center , Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455 , USA . Email: truhlar@umn.edu ; Email: gagliard@umn.edu.
  • 2019-03-08
Published in:
  • Chemical science. - 2019
General Chemistry
English 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.
Language
  • English
Open access status
gold
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Persistent URL
https://sonar.ch/global/documents/265702
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