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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Resumé

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.

OriginalsprogEngelsk
Artikelnummer124113
TidsskriftJournal of Chemical Physics
Vol/bind151
Udgave nummer12
ISSN0021-9606
DOI
StatusUdgivet - 2019

Fingeraftryk

Excitation energy
atomic energy levels
Density functional theory
density functional theory
energy
Wave functions
approximation
functionals
perturbation theory
wave functions
deviation
Molecules
molecules

Citer dette

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title = "Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations",
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.",
author = "Kjellgren, {Erik Rosendahl} and Hedeg{\aa}rd, {Erik Donovan} and Jensen, {Hans J{\o}rgen Aagaard}",
year = "2019",
doi = "10.1063/1.5119312",
language = "English",
volume = "151",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics",
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Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations. / Kjellgren, Erik Rosendahl; Hedegård, Erik Donovan; Jensen, Hans Jørgen Aagaard.

I: Journal of Chemical Physics, Bind 151, Nr. 12, 124113, 2019.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations

AU - Kjellgren, Erik Rosendahl

AU - Hedegård, Erik Donovan

AU - Jensen, Hans Jørgen Aagaard

PY - 2019

Y1 - 2019

N2 - 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.

AB - 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.

U2 - 10.1063/1.5119312

DO - 10.1063/1.5119312

M3 - Journal article

VL - 151

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 12

M1 - 124113

ER -