Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations

Erik Rosendahl Kjellgren, Erik Donovan Hedegård, Hans Jørgen Aagaard Jensen

Research output: Contribution to journalArticlepeer-review

4 Citations (SciVal)

Abstract

Linear response theory for the multiconfigurational short-range density functional theory (MC-srDFT) model is extended to triplet response with a singlet reference wave function. The triplet linear response equations for MC-srDFT are derived for a general hybrid srGGA functional and implemented in the Dalton program. Triplet excitation energies are benchmarked against the CC3 model of coupled cluster theory and the complete-active-space second-order perturbation theory using three different short-range functionals (srLDA, srPBE, and srPBE0), both with full linear response and employing the generalized Tamm-Dancoff approximation (gTDA). We find that using gTDA is required for obtaining reliable triplet excitations; for the CAS-srPBE model, the mean absolute deviation decreases from 0.40 eV to 0.26 eV, and for the CAS-srLDA model, it decreases from 0.29 eV to 0.21 eV. As expected, the CAS-srDFT model is found to be superior to the HF-srDFT model when analyzing the calculated triplet excitations for molecules in the benchmark set where increased static correlation is expected.

Original languageEnglish
Article number124113
JournalJournal of Chemical Physics
Volume151
Issue number12
DOIs
Publication statusPublished - 2019 Sep 28

Subject classification (UKÄ)

  • Theoretical Chemistry

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