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.
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Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations
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28 September 2019
Research Article|
September 27 2019
Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations
Erik Rosendahl Kjellgren
;
Erik Rosendahl Kjellgren
1
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, DK-5230 Odense M, Denmark
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Erik Donovan Hedegård
;
Erik Donovan Hedegård
2
Division of Theoretical Chemistry, Lund University
, Kemicentrum P.O. Box 124, SE-221 00 Lund, Sweden
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Hans Jørgen Aagaard Jensen
Hans Jørgen Aagaard Jensen
a)
1
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, DK-5230 Odense M, Denmark
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a)
Electronic mail: hjj@sdu.dk
J. Chem. Phys. 151, 124113 (2019)
Article history
Received:
July 10 2019
Accepted:
September 04 2019
Citation
Erik Rosendahl Kjellgren, Erik Donovan Hedegård, Hans Jørgen Aagaard Jensen; Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations. J. Chem. Phys. 28 September 2019; 151 (12): 124113. https://doi.org/10.1063/1.5119312
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