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

Summary, in English

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.

• Author: Erik Rosendahl Kjellgren; Erik Donovan Hedegård; Hans Jørgen Aagaard Jensen
• Department/s: Computational Chemistry
• Publishing year: 2019-09-28
• Language: English
• Publication/Series: Journal of Chemical Physics
• Volume: 151
• Issue: 12
• Links: http://dx.doi.org/10.1063/1.5119312
• Document type: Journal article
• Publisher: American Institute of Physics (AIP)
• Topic: Theoretical Chemistry (including Computational Chemistry)
• Status: Published
• ISBN/ISSN/Other: ISSN: 0021-9606