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The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules
Factors influencing the rate of reverse intersystem crossing (k (rISC)) in thermally activated delayed fluorescence (TADF) emitters are critical for improving the efficiency and performance of third‐generation heavy‐metal‐free organic light‐emitting diodes (OLEDs). However, present understanding of...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5096030/ https://www.ncbi.nlm.nih.gov/pubmed/27338655 http://dx.doi.org/10.1002/cphc.201600662 |
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author | Gibson, Jamie Monkman, Andrew P. Penfold, Thomas J. |
author_facet | Gibson, Jamie Monkman, Andrew P. Penfold, Thomas J. |
author_sort | Gibson, Jamie |
collection | PubMed |
description | Factors influencing the rate of reverse intersystem crossing (k (rISC)) in thermally activated delayed fluorescence (TADF) emitters are critical for improving the efficiency and performance of third‐generation heavy‐metal‐free organic light‐emitting diodes (OLEDs). However, present understanding of the TADF mechanism does not extend far beyond a thermal equilibrium between the lowest singlet and triplet states and consequently research has focused almost exclusively on the energy gap between these two states. Herein, we use a model spin‐vibronic Hamiltonian to reveal the crucial role of non‐Born‐Oppenheimer effects in determining k (rISC). We demonstrate that vibronic (nonadiabatic) coupling between the lowest local excitation triplet ((3)LE) and lowest charge transfer triplet ((3)CT) opens the possibility for significant second‐order coupling effects and increases k (rISC) by about four orders of magnitude. Crucially, these simulations reveal the dynamical mechanism for highly efficient TADF and opens design routes that go beyond the Born‐Oppenheimer approximation for the future development of high‐performing systems. |
format | Online Article Text |
id | pubmed-5096030 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-50960302016-11-09 The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules Gibson, Jamie Monkman, Andrew P. Penfold, Thomas J. Chemphyschem Communications Factors influencing the rate of reverse intersystem crossing (k (rISC)) in thermally activated delayed fluorescence (TADF) emitters are critical for improving the efficiency and performance of third‐generation heavy‐metal‐free organic light‐emitting diodes (OLEDs). However, present understanding of the TADF mechanism does not extend far beyond a thermal equilibrium between the lowest singlet and triplet states and consequently research has focused almost exclusively on the energy gap between these two states. Herein, we use a model spin‐vibronic Hamiltonian to reveal the crucial role of non‐Born‐Oppenheimer effects in determining k (rISC). We demonstrate that vibronic (nonadiabatic) coupling between the lowest local excitation triplet ((3)LE) and lowest charge transfer triplet ((3)CT) opens the possibility for significant second‐order coupling effects and increases k (rISC) by about four orders of magnitude. Crucially, these simulations reveal the dynamical mechanism for highly efficient TADF and opens design routes that go beyond the Born‐Oppenheimer approximation for the future development of high‐performing systems. John Wiley and Sons Inc. 2016-07-26 2016-10-05 /pmc/articles/PMC5096030/ /pubmed/27338655 http://dx.doi.org/10.1002/cphc.201600662 Text en ©2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Gibson, Jamie Monkman, Andrew P. Penfold, Thomas J. The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title | The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title_full | The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title_fullStr | The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title_full_unstemmed | The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title_short | The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules |
title_sort | importance of vibronic coupling for efficient reverse intersystem crossing in thermally activated delayed fluorescence molecules |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5096030/ https://www.ncbi.nlm.nih.gov/pubmed/27338655 http://dx.doi.org/10.1002/cphc.201600662 |
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