Manian, A., Shaw, R.A. orcid.org/0000-0002-9977-0835, Lyskov, I. et al. (2 more authors) (2021) Modeling radiative and non-radiative pathways at both the Franck–Condon and Herzberg–Teller approximation level. The Journal of Chemical Physics, 155 (5). 054108. ISSN 0021-9606
Abstract
Here, we present a concise model that can predict the photoluminescent properties of a given compound from first principles, both within and beyond the Franck–Condon approximation. The formalism required to compute fluorescence, Internal Conversion (IC), and Inter-System Crossing (ISC) is discussed. The IC mechanism, in particular, is a difficult pathway to compute due to difficulties associated with the computation of required bosonic configurations and non-adiabatic coupling elements. Here, we offer a discussion and breakdown on how to model these pathways at the Density Functional Theory (DFT) level with respect to its computational implementation, strengths, and current limitations. The model is then used to compute the photoluminescent quantum yield (PLQY) of a number of small but important compounds: anthracene, tetracene, pentacene, diketo-pyrrolo-pyrrole (DPP), and Perylene Diimide (PDI) within a polarizable continuum model. Rate constants for fluorescence, IC, and ISC compare well for the most part with respect to experiment, despite triplet energies being overestimated to a degree. The resulting PLQYs are promising with respect to the level of theory being DFT. While we obtained a positive result for PDI within the Franck–Condon limit, the other systems require a second order correction. Recomputing quantum yields with Herzberg–Teller terms yields PLQYs of 0.19, 0.08, 0.04, 0.70, and 0.99 for anthracene, tetracene, pentacene, DPP, and PDI, respectively. Based on these results, we are confident that the presented methodology is sound with respect to the level of quantum chemistry and presents an important stepping stone in the search for a tool to predict the properties of larger coupled systems.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2021 The Authors. This is an author-produced version of a paper subsequently published in The Journal of Chemical Physics. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 10 Aug 2021 07:19 |
Last Modified: | 11 Aug 2021 01:27 |
Status: | Published |
Publisher: | AIP Publishing |
Refereed: | Yes |
Identification Number: | 10.1063/5.0058643 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:176928 |