Prediction of Excited-State Energies and Singlet–Triplet Gaps of Charge-Transfer States Using a Restricted Open-Shell Kohn–Sham Approach
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Author(s)
Hait, Diptarka
Zhu, Tianyu
McMahon, David Paul
Van Voorhis, Troy
Date Issued
June 2016
Journal
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Citation
Hait, Diptarka et al. “Prediction of Excited-State Energies and Singlet–Triplet Gaps of Charge-Transfer States Using a Restricted Open-Shell Kohn–Sham Approach.” Journal of Chemical Theory and Computation 12, 7 (June 2016): 3353–3359 © 2016 American Chemical Society
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Author's final manuscript
Abstract
Organic molecules with charge-transfer (CT) excited states are widely used in industry and are especially attractive as candidates for fabrication of energy efficient OLEDs, as they can harvest energy from nonradiative triplets by means of thermally activated delayed fluorescence (TADF). It is therefore useful to have computational protocols for accurate estimation of their electronic spectra in order to screen candidate molecules for OLED applications. However, it is difficult to predict the photophysical properties of TADF molecules with LR-TDDFT, as semilocal LR-TDDFT is incapable of accurately modeling CT states. Herein, we study absorption energies, emission energies, zero–zero transition energies, and singlet–triplet gaps of TADF molecules using a restricted open-shell Kohn–Sham (ROKS) approach instead and discover that ROKS calculations with semilocal hybrid functionals are in good agreement with experiments—unlike TDDFT, which significantly underestimates energy gaps. We also propose a cheap computational protocol for studying excited states with large CT character that is found to give good agreement with experimental results without having to perform any excited-state geometry optimizations.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acs.jctc.6b00426
