Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations
(2019) In Journal of Chemical Physics 151(12).- 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... (More)
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.
(Less)
- author
- Kjellgren, Erik Rosendahl ; Hedegård, Erik Donovan LU and Jensen, Hans Jørgen Aagaard
- organization
- publishing date
- 2019-09-28
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 151
- issue
- 12
- article number
- 124113
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- scopus:85072750309
- pmid:31575161
- ISSN
- 0021-9606
- DOI
- 10.1063/1.5119312
- language
- English
- LU publication?
- yes
- id
- 4491efcc-e1d1-4ede-9988-86c892a5b9b1
- date added to LUP
- 2022-03-30 16:04:23
- date last changed
- 2024-05-10 07:36:13
@article{4491efcc-e1d1-4ede-9988-86c892a5b9b1,
abstract = {{<p>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.</p>}},
author = {{Kjellgren, Erik Rosendahl and Hedegård, Erik Donovan and Jensen, Hans Jørgen Aagaard}},
issn = {{0021-9606}},
language = {{eng}},
month = {{09}},
number = {{12}},
publisher = {{American Institute of Physics (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Triplet excitation energies from multiconfigurational short-range density-functional theory response calculations}},
url = {{http://dx.doi.org/10.1063/1.5119312}},
doi = {{10.1063/1.5119312}},
volume = {{151}},
year = {{2019}},
}