| Texto completo | |
| Autor(es): |
Ribeiro, R. B.
;
Varella, M. T. do N.
Número total de Autores: 2
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Physical Chemistry Chemical Physics; v. 26, n. 17, p. 13-pg., 2024-04-05. |
| Resumo | |
Understanding charge transfer processes is essential to estimate the performance of organic photovoltaic technologies. Although experimental production is on the rise, predictability strongly relies on theoretical modeling, which is limited to the size of semiconductors. As a computationally favorable approach, we benchmarked the long-range corrected (LC) time-dependent (TD) formulation of the semi-empirical density functional-based tight-binding method (DFTB) for three polycyclic aromatic hydrocarbons (PAHs) and studied the DTP-IC-4Ph molecule, a PAH-based non-fullerene electron acceptor (NFA) with an A-D-A backbone structure. After a thorough investigation into the long-range parameter (omega) tuning for naphthalene, anthracene and pyrene, the excitation energies, oscillator strengths and Natural Transition Orbitals (NTOs) were compared with the standard omega B97X-D/6-31G(d,p) level of theory and the ADC2/6-31G(d,p) multiconfigurational method. We estimated mobility-related properties of the NFA and considered 1000 thermally accessible configurations to qualitatively reproduce the experimental absorption profile and investigate the energetic disorder. Finally, we conducted a fragment-based analysis using the one-electron transition density matrix (1TDM) to determine the character of the excited states and investigate the effect of side chains on exciton formation. Our results are sensitive to the level of theory and highly dependent on the long-range parameter but suggest that the presence of alkyl chains promotes a higher average charge delocalization and allows for additional hopping mechanisms, favoring the charge transfer dynamics. Benchmark of LC-TD-DFTB to investigate the excited state properties of a non-fullerene electron acceptor. The tight-binding method is highly dependent on the long-range parameter but reproduced LC-TD-DFT results and experimental absorption spectra. (AU) | |
| Processo FAPESP: | 22/04379-3 - Células Solares Orgânicas baseadas em Aceitadores Não-fulerênicos: Da formação do éxciton à mobilidade de carga |
| Beneficiário: | Rafael Bicudo Ribeiro |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado |
| Processo FAPESP: | 20/16155-7 - Modelos moleculares para ciências positrônica, biológica e de materiais |
| Beneficiário: | Márcio Teixeira do Nascimento Varella |
| Modalidade de apoio: | Auxílio à Pesquisa - Regular |