2019/02/25 by Michele Guerrini, Caterina Cocchi, Arrigo Calzolari +2 · 29 citations
Chemistry · Physics and Astronomy · #Aggregate (composite) #Character (mathematics) #Charge (physics) #Chemical physics #Chemistry #Computational chemistry #Density functional theory #Excitation #Intermolecular force #Intramolecular force #J-aggregate #Materials science #Molecule #Nanotechnology #Optoelectronics #Organic semiconductor #Physics #Quantum mechanics #Quantum, superfluid, helium dynamics #Semiconductor #Spectroscopy and Laser Applications #Spectroscopy and Quantum Chemical Studies #cond-mat.mtrl-sci #physics.chem-ph
paper · pdf · doi:10.1021/acs.jpcc.8b11709
published in The Journal of Physical Chemistry C 123(11), 6831-6838 (American Chemical Society) · published under ACS Authorchoice license
openalex publication_date 2019/02/25 · arxiv created 2019/04/24 · arxiv updated 2019/04/25 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
In a first-principles study based on density functional theory and many-body perturbation theory, we address the interplay between intra- and intermolecular interactions in a J-aggregate formed by push-pull organic dyes by investigating its electronic and optical properties. We find that the most intense excitation dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a combination of intramolecular charge transfer, coming from the push-pull character of the constituting dyes, and intermolecular charge transfer, due to the dense molecular packing. We also show the presence of a pure intermolecular charge-transfer excitation within the J-band, which is expected to play a relevant role in the emission properties of the J-aggregate. Our results shed light on the microscopic character of optical excitations of J-aggregates and offer new perspectives to further understand the nature of collective excitations in organic semiconductors.