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Title: Electronic couplings for singlet fission: Orbital choice and extrapolation to the complete basis set limit

Abstract

For the search for promising singlet fission candidates, the calculation of the effective electronic coupling, which is required to estimate the singlet fission rate between the initially excited state (S0S1) and the multiexcitonic state (1TT, two triplets on neighboring molecules, coupled into a singlet), should be sufficiently reliable and fast enough to explore the configuration space. We propose here to modify the calculation of the effective electronic coupling using a nonorthogonal configuration interaction approach by: (a) using only one set of orbitals, optimized for the triplet state of the molecules, to describe all molecular electronic states, and (b) only taking the leading configurations into consideration. Furthermore, we also studied the basis set convergence of the electronic coupling, and we found, by comparison to the complete basis set limit obtained using the cc-pVnZ series of basis sets, that both the aug-ccpVDZ and 6–311++G** basis sets are a good compromise between accuracy and computational feasibility. The proposed approach enables future work on larger clusters of molecules than dimers.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]
  1. Stratingh Institute for Chemistry University of Groningen Groningen The Netherlands
  2. High Performance Computing Group SURFSara Amsterdam The Netherlands
  3. Zernike Institute for Advanced Materials University of Groningen Groningen The Netherlands
  4. Stratingh Institute for Chemistry University of Groningen Groningen The Netherlands, Zernike Institute for Advanced Materials University of Groningen Groningen The Netherlands, Department of Inorganic and Physical Chemistry Ghent University Ghent Belgium
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1734589
Alternate Identifier(s):
OSTI ID: 1786470; OSTI ID: 1817075
Grant/Contract Number:  
DE‐AC05‐00OR22725; AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Journal of Computational Chemistry
Additional Journal Information:
Journal Name: Journal of Computational Chemistry Journal Volume: 42 Journal Issue: 5; Journal ID: ISSN 0192-8651
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING; basis set limit; effective electronic coupling; nonorthogonal configuration interaction; singlet fission

Citation Formats

Speelman, Tom, Cunha, Ana V., Kathir, R. K., and Havenith, Remco W. A.. Electronic couplings for singlet fission: Orbital choice and extrapolation to the complete basis set limit. United States: N. p., 2020. Web. https://doi.org/10.1002/jcc.26458.
Speelman, Tom, Cunha, Ana V., Kathir, R. K., & Havenith, Remco W. A.. Electronic couplings for singlet fission: Orbital choice and extrapolation to the complete basis set limit. United States. https://doi.org/10.1002/jcc.26458
Speelman, Tom, Cunha, Ana V., Kathir, R. K., and Havenith, Remco W. A.. Tue . "Electronic couplings for singlet fission: Orbital choice and extrapolation to the complete basis set limit". United States. https://doi.org/10.1002/jcc.26458.
@article{osti_1734589,
title = {Electronic couplings for singlet fission: Orbital choice and extrapolation to the complete basis set limit},
author = {Speelman, Tom and Cunha, Ana V. and Kathir, R. K. and Havenith, Remco W. A.},
abstractNote = {For the search for promising singlet fission candidates, the calculation of the effective electronic coupling, which is required to estimate the singlet fission rate between the initially excited state (S0S1) and the multiexcitonic state (1TT, two triplets on neighboring molecules, coupled into a singlet), should be sufficiently reliable and fast enough to explore the configuration space. We propose here to modify the calculation of the effective electronic coupling using a nonorthogonal configuration interaction approach by: (a) using only one set of orbitals, optimized for the triplet state of the molecules, to describe all molecular electronic states, and (b) only taking the leading configurations into consideration. Furthermore, we also studied the basis set convergence of the electronic coupling, and we found, by comparison to the complete basis set limit obtained using the cc-pVnZ series of basis sets, that both the aug-ccpVDZ and 6–311++G** basis sets are a good compromise between accuracy and computational feasibility. The proposed approach enables future work on larger clusters of molecules than dimers.},
doi = {10.1002/jcc.26458},
journal = {Journal of Computational Chemistry},
number = 5,
volume = 42,
place = {United States},
year = {2020},
month = {12}
}

Journal Article:
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https://doi.org/10.1002/jcc.26458

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