The Importance of Vibronic Coupling for Efficient Reverse Intersystem Crossing in Thermally Activated Delayed Fluorescence Molecules
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- Jamie Gibson
- School of Chemistry Newcastle University Newcastle upon Tyne NE1 7RU UK
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- Andrew P. Monkman
- School of Physics University of Durham Durham DH1 3LE UK
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- Thomas J. Penfold
- School of Chemistry Newcastle University Newcastle upon Tyne NE1 7RU UK
書誌事項
- 公開日
- 2016-07-26
- 権利情報
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- http://creativecommons.org/licenses/by/4.0/
- DOI
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- 10.1002/cphc.201600662
- 公開者
- Wiley
この論文をさがす
説明
<jats:title>Abstract</jats:title><jats:p>Factors influencing the rate of reverse intersystem crossing (<jats:italic>k</jats:italic><jats:sub>rISC</jats:sub>) 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 <jats:italic>k</jats:italic><jats:sub>rISC</jats:sub>. We demonstrate that vibronic (nonadiabatic) coupling between the lowest local excitation triplet (<jats:sup>3</jats:sup>LE) and lowest charge transfer triplet (<jats:sup>3</jats:sup>CT) opens the possibility for significant second‐order coupling effects and increases <jats:italic>k</jats:italic><jats:sub>rISC</jats:sub> 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.</jats:p>
収録刊行物
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- ChemPhysChem
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ChemPhysChem 17 (19), 2956-2961, 2016-07-26
Wiley
