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Title: Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”

The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals led to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.
Authors:
ORCiD logo [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. Univ. at Buffalo, State Univ. of New York, Buffalo, NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Report Number(s):
PNNL-SA-125649
Journal ID: ISSN 2191-1363; 49665; KP1704020
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
ChemistryOpen
Additional Journal Information:
Journal Volume: 6; Journal Issue: 3; Journal ID: ISSN 2191-1363
Publisher:
ChemPubSoc Europe
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electronic structure theory; Environmental Molecular Sciences Laboratory; chromophores; computational chemistry; density functional calculations; electronic spectra; heterocycles
OSTI Identifier:
1371988

Moore, II, Barry, Schrader, Robert L., Kowalski, Karol, and Autschbach, Jochen. Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”. United States: N. p., Web. doi:10.1002/open.201700046.
Moore, II, Barry, Schrader, Robert L., Kowalski, Karol, & Autschbach, Jochen. Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”. United States. doi:10.1002/open.201700046.
Moore, II, Barry, Schrader, Robert L., Kowalski, Karol, and Autschbach, Jochen. 2017. "Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”". United States. doi:10.1002/open.201700046. https://www.osti.gov/servlets/purl/1371988.
@article{osti_1371988,
title = {Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”},
author = {Moore, II, Barry and Schrader, Robert L. and Kowalski, Karol and Autschbach, Jochen},
abstractNote = {The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals led to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.},
doi = {10.1002/open.201700046},
journal = {ChemistryOpen},
number = 3,
volume = 6,
place = {United States},
year = {2017},
month = {5}
}

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