Elucidating the Electronic Structure of a Delayed Fluorescence Emitter via Orbital Interactions, Excitation Energy Components, Charge-Transfer Numbers, and Vibrational Reorganization Energies.
Zheng Pei,Qi Ou,Yuezhi Mao,Junjie Yang,Aurélien de la Lande,Felix Plasser,WanZhen Liang,Zhigang Shuai,Yihan Shao +8 more
Reads0
Chats0
TLDR
Wang et al. as discussed by the authors employed four advanced electronic structure analysis tools, including absolutely localized molecular orbitals (ALMO)-based analysis, excitation energy component analysis, charge transfer number analysis, and vibrational reorganization energy analysis, which is extended to use fragment-based Hirshfeld weights.Abstract:
Recently, Wang and co-workers carried out frontier molecule orbital engineering in the design of m-Cz-BNCz, a thermally activated delayed fluorescence (TADF) molecule that emits pure green light at an external quantum efficiency of 27%. To further understand the underlying molecular design principles, we employed four advanced electronic structure analysis tools. First, an absolutely localized molecular orbitals (ALMO-) based analysis indicates an antibonding combination between the highest occupied molecular orbitals (HOMOs) of the donor 3,6-di-tert-butylcarbazole fragment and the acceptor BNCz fragment, which raises the HOMO energy and red-shifts the fluorescence emission wavelength. Second, excitation energy component analysis reveals that the S1-T1 gap is dominated by two-electron components of the excitation energies. Third, charge transfer number analysis, which is extended to use fragment-based Hirshfeld weights, indicates that the S1 and T1 excited states of m-Cz-BNCz (within time-dependent density functional theory) have notable charge transfer characters (27% for S1 and 12% for T1). This provides a balance between a small single-triplet gap and a substantial fluorescence intensity. Last, a vibrational reorganization energy analysis pinpoints the torsional motion between the BNCz and Cz moieties of m-Cz-BNCz as the source for its wider emission peak than that of p-Cz-BNCz. These four types of analyses are expected to be very valuable in the study and design of other TADF and functional dye molecules.read more
Citations
More filters
Journal ArticleDOI
Precise Functionalization of a Multiple‐Resonance Framework: Constructing Narrowband Organic Electroluminescent Materials with External Quantum Efficiency over 40%
TL;DR: In this article , a synthetic methodology is demonstrated for functionalizing brominated B�N-containing multiple resonance (MR) frameworks with multifarious functional groups, such as donors, acceptors, and moieties without obvious push-pull electron properties.
Journal ArticleDOI
PCM-ROKS for the Description of Charge-Transfer States in Solution: Singlet-Triplet Gaps with Chemical Accuracy from Open-Shell Kohn-Sham Reaction-Field Calculations.
TL;DR: In this paper, an approach that combines spin-unrestricted (UKS) and restricted open-shell Kohn-Sham (ROKS) self-consistent field calculations with a polarizable-continuum model and range-separated hybrid functionals is presented.
Journal ArticleDOI
Thermally Activated Delayed Fluorescence Mechanism of a Bicyclic "Carbene-Metal-Amide" Copper Compound: DFT/MRCI Studies and Roles of Excited-State Structure Relaxation.
TL;DR: In this article , the authors investigated the luminescence mechanism of one "carbene-metal-amide" copper compound with thermally activated delayed fluorescence (TADF) using density functional theory (DFT)/multireference configuration interaction, DFT, and time-dependent DFT methods with the polarizable continuum model.
Journal ArticleDOI
Evaluation of molecular photophysical and photochemical properties using linear response time-dependent density functional theory with classical embedding: Successes and challenges.
TL;DR: In this paper , the Tamm-Dancoff approximation to TDDFT, spin-flip DFT, and spin-adiabatic DFT are discussed, with a specific emphasis on the implementation of analytical energy derivatives for various radiative and radiativeless transition processes among electronic states.
Journal ArticleDOI
The role of excited-state character, structural relaxation, and symmetry breaking in enabling delayed fluorescence activity in push-pull chromophores.
TL;DR: In this paper, a detailed analysis of the excited states at a correlated ab initio level highlights the presence of a number of closely spaced singlet and triplet states of varying character.
References
More filters
Journal ArticleDOI
Highly efficient organic light-emitting diodes from delayed fluorescence
Hiroki Uoyama,Kenichi Goushi,Kenichi Goushi,Katsuyuki Shizu,Hiroko Nomura,Chihaya Adachi,Chihaya Adachi +6 more
TL;DR: A class of metal-free organic electroluminescent molecules in which the energy gap between the singlet and triplet excited states is minimized by design, thereby promoting highly efficient spin up-conversion from non-radiative triplet states to radiative singlet states while maintaining high radiative decay rates.
Journal ArticleDOI
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
Yihan Shao,Zhengting Gan,Evgeny Epifanovsky,Andrew T. B. Gilbert,Michael Wormit,Joerg Kussmann,Adrian W. Lange,Andrew Behn,Jia Deng,Xintian Feng,Debashree Ghosh,Matthew Goldey,Paul R. Horn,Leif D. Jacobson,Ilya Kaliman,Rustam Z. Khaliullin,Tomasz Kuś,Arie Landau,Jie Liu,Emil Proynov,Young Min Rhee,Ryan M. Richard,Mary A. Rohrdanz,Ryan P. Steele,Eric J. Sundstrom,H. Lee Woodcock,Paul M. Zimmerman,Dmitry Zuev,Ben Albrecht,Ethan Alguire,Brian J. Austin,Gregory J. O. Beran,Yves A. Bernard,Eric J. Berquist,Kai Brandhorst,Ksenia B. Bravaya,Shawn T. Brown,David Casanova,Chun-Min Chang,Yunqing Chen,Siu Hung Chien,Kristina D. Closser,Deborah L. Crittenden,Michael Diedenhofen,Robert A. DiStasio,Hainam Do,Anthony D. Dutoi,Richard G. Edgar,Shervin Fatehi,Laszlo Fusti-Molnar,An Ghysels,Anna Golubeva-Zadorozhnaya,Joseph Gomes,Magnus W. D. Hanson-Heine,Philipp H. P. Harbach,Andreas W. Hauser,Edward G. Hohenstein,Zachary C. Holden,Thomas-C. Jagau,Hyunjun Ji,Benjamin Kaduk,Kirill Khistyaev,Jae-Hoon Kim,Jihan Kim,Rollin A. King,Phil Klunzinger,Dmytro Kosenkov,Tim Kowalczyk,Caroline M. Krauter,Ka Un Lao,Adèle D. Laurent,Keith V. Lawler,Sergey V. Levchenko,Ching Yeh Lin,Fenglai Liu,Ester Livshits,Rohini C. Lochan,Arne Luenser,Prashant Uday Manohar,Samuel F. Manzer,Shan-Ping Mao,Narbe Mardirossian,Aleksandr V. Marenich,Simon A. Maurer,Nicholas J. Mayhall,Eric Neuscamman,C. Melania Oana,Roberto Olivares-Amaya,Darragh P. O’Neill,John Parkhill,Trilisa M. Perrine,Roberto Peverati,Alexander Prociuk,Dirk R. Rehn,Edina Rosta,Nicholas J. Russ,Shaama Mallikarjun Sharada,Sandeep Sharma,David W. Small,Alexander J. Sodt,Tamar Stein,David Stück,Yu-Chuan Su,Alex J. W. Thom,Takashi Tsuchimochi,Vitalii Vanovschi,Leslie Vogt,Oleg A. Vydrov,Tao Wang,Mark A. Watson,Jan Wenzel,Alec F. White,Christopher F. Williams,Jun Yang,Sina Yeganeh,Shane R. Yost,Zhi-Qiang You,Igor Ying Zhang,Xing Zhang,Yan Zhao,Bernard R. Brooks,Garnet Kin-Lic Chan,Daniel M. Chipman,Christopher J. Cramer,William A. Goddard,Mark S. Gordon,Warren J. Hehre,Andreas Klamt,Henry F. Schaefer,Michael W. Schmidt,C. David Sherrill,Donald G. Truhlar,Arieh Warshel,Xin Xu,Alán Aspuru-Guzik,Roi Baer,Alexis T. Bell,Nicholas A. Besley,Jeng-Da Chai,Andreas Dreuw,Barry D. Dunietz,Thomas R. Furlani,Steven R. Gwaltney,Chao-Ping Hsu,Yousung Jung,Jing Kong,Daniel S. Lambrecht,WanZhen Liang,Christian Ochsenfeld,Vitaly A. Rassolov,Lyudmila V. Slipchenko,Joseph E. Subotnik,Troy Van Voorhis,John M. Herbert,Anna I. Krylov,Peter Gill,Martin Head-Gordon +156 more
TL;DR: A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided in this paper, covering approximately the last seven years, including developments in density functional theory and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces.
Journal ArticleDOI
Recent advances in organic thermally activated delayed fluorescence materials.
Zhiyong Yang,Zhu Mao,Zongliang Xie,Yi Zhang,Siwei Liu,Juan Zhao,Jiarui Xu,Zhenguo Chi,Matthew P. Aldred +8 more
TL;DR: This review summarizes and discusses the latest progress concerning this rapidly developing research field, in which the majority of the reported TADF systems are discussed, along with their derived structure-property relationships, TadF mechanisms and applications.
Journal ArticleDOI
Thermally Activated Delayed Fluorescence Materials Towards the Breakthrough of Organoelectronics
Ye Tao,Kai Yuan,Ting Chen,Peng Xu,Huanhuan Li,Runfeng Chen,Chao Zheng,Lei Zhang,Wei Huang,Wei Huang +9 more
TL;DR: An overview of the quick development in TADF mechanisms, materials, and applications is presented, with a particular emphasis on their different types of metal-organic complexes, D-A molecules, and fullerenes.
Journal ArticleDOI
Design of Efficient Thermally Activated Delayed Fluorescence Materials for Pure Blue Organic Light Emitting Diodes
Qisheng Zhang,Jie Li,Katsuyuki Shizu,Shuping Huang,Shuzo Hirata,Hiroshi Miyazaki,Chihaya Adachi +6 more
TL;DR: TADF has been characterized for a carbazole/sulfone derivative in both solutions and doped films and a pure blue organic light emitting diode (OLED) based on this compound demonstrates a very high external quantum efficiency (EQE) of nearly 10% at low current density.