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

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

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Sammanfattning

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.

Originalspråkengelska
Artikelnummer124113
TidskriftJournal of Chemical Physics
Volym151
Utgåva12
DOI
StatusPublished - 2019 sep. 28

Ämnesklassifikation (UKÄ)

  • Teoretisk kemi

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