RESUMO
Triplet harvesting processes are essential for enhancing efficiencies of fluorescent organic light-emitting diodes. Besides more conventional thermally activated delayed fluorescence and triplet-triplet annihilation, the hot exciton mechanism has been recently noticed because it helps reduce the efficiency roll-off and improve device stability. Hot exciton materials enable the conversion of triplet excitons to singlet ones via reverse inter-system crossing from high-lying triplet states and thereby the depopulation of long-lived triplet excitons that are prone to chemical and/or efficiency degradation. Although their anti-Kasha characteristics have not been clearly explained, numerous molecules with behaviors assigned to the hot exciton mechanism have been reported. Indeed, the related developments appear to have just passed the stage of infancy now, and there will likely be more roles that computational elucidations can play. With this perspective in mind, we review some selected experimental studies on the mechanism and the related designs and then on computational studies. On the computational side, we examine what has been found and what is still missing with regard to properly understanding this interesting mechanism. We further discuss potential future points of computational interests toward aiming for eventually presenting in silico design guides.
Assuntos
Corantes , FluorescênciaRESUMO
OBJECTIVES: Electrocardiography (ECG)-based diagnosis by experts cannot maintain uniform quality because individual differences may occur. Previous public databases can be used for clinical studies, but there is no common standard that would allow databases to be combined. For this reason, it is difficult to conduct research that derives results by combining databases. Recent commercial ECG machines offer diagnoses similar to those of a physician. Therefore, the purpose of this study was to construct a standardized ECG database using computerized diagnoses. METHODS: The constructed database was standardized using Systematized Nomenclature of Medicine Clinical Terms (SNOMED CT) and Observational Medical Outcomes Partnership-common data model (OMOP-CDM), and data were then categorized into 10 groups based on the Minnesota classification. In addition, to extract high-quality waveforms, poor-quality ECGs were removed, and database bias was minimized by extracting at least 2,000 cases for each group. To check database quality, the difference in baseline displacement according to whether poor ECGs were removed was analyzed, and the usefulness of the database was verified with seven classification models using waveforms. RESULTS: The standardized KURIAS-ECG database consists of high-quality ECGs from 13,862 patients, with about 20,000 data points, making it possible to obtain more than 2,000 for each Minnesota classification. An artificial intelligence classification model using the data extracted through SNOMED-CT showed an average accuracy of 88.03%. CONCLUSIONS: The KURIAS-ECG database contains standardized ECG data extracted from various machines. The proposed protocol should promote cardiovascular disease research using big data and artificial intelligence.
RESUMO
Minimizing the energy difference between the lowest singlet (S1) and the lowest triplet states, ΔEST, is the main strategy to design thermally activated delayed fluorescence (TADF) molecules, and spatially separating the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is the general method in the design. However, such a separation also tends to reduce the oscillator strength of the S1 state. In real systems, vibrations change the S1 oscillator strength, and thus one needs to consider the vibronic coupling toward searching for TADF candidate molecules. Here, we evaluate the importance of vibronic coupling by including the first-order perturbative correction to the transition dipole moments of carbazolyl-phthalonitrile derivatives. Indeed, some molecules display large enhancements in their oscillator strengths, with their fluorescence lifetimes reduced by 2 orders of magnitude. The twisting mode between the carbazole groups and phthalonitrile is the most important mode in inducing the perturbations. Thus, performing the perturbative correction is crucial in attaining more reliable predictions on their fluorescence propensities. We also observe that some other molecules, whose zeroth-order predicted fluorescence rates are much slower than the actual experimental data, are affected little by the same first-order correction. For these molecules, we deduce that the geometry-dependent excited-state switching kicks in. Our results demonstrate the significance of vibronic coupling in TADF molecules and the importance of adopting correction schemes as the guidelines for screening of useful TADF molecules.
