Noniterative Doubles Corrections to the Random Phase and Higher Random Phase Approximations: Singlet and Triplet Excitation Energies

Pi A. B. Haase*, Rasmus Faber, Patricio F. Provasi, Stephan P. A. Sauer

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

12 Citations (Scopus)
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Abstract

The second-order noniterative doubles-corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles-corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second-order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second-order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time.

Original languageEnglish
Pages (from-to)43-55
Number of pages13
JournalJournal of Computational Chemistry
Volume41
Issue number1
DOIs
Publication statusPublished - 5-Jan-2020

Keywords

  • RPA(D)
  • HRPA(D)
  • singlet
  • triplet
  • excited states
  • OF-MOTION METHOD
  • POLARIZATION PROPAGATOR CALCULATIONS
  • ELECTRONICALLY EXCITED-STATES
  • DENSITY-FUNCTIONAL THEORY
  • COUPLED-CLUSTER SINGLES
  • GAUSSIAN-BASIS SETS
  • HARTREE-FOCK
  • ATOMS LI
  • EQUATIONS
  • BENCHMARKS

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