Intermolecular Interactions and Charge Resonance Contributions to Triplet and Singlet Exciton States of Oligoacene Aggregates
dc.contributor.author | Dai, Yasi | |
dc.contributor.author | Calzolari, Alessandro | |
dc.contributor.author | Zubiria Ulacia, María | |
dc.contributor.author | Casanova Casas, David | |
dc.contributor.author | Negri, Fabrizia | |
dc.date.accessioned | 2023-03-01T13:22:26Z | |
dc.date.available | 2023-03-01T13:22:26Z | |
dc.date.issued | 2022-12-23 | |
dc.identifier.citation | Molecules 28(1) : (2023) // Article ID 119 | es_ES |
dc.identifier.issn | 1420-3049 | |
dc.identifier.uri | http://hdl.handle.net/10810/60199 | |
dc.description.abstract | Intermolecular interactions modulate the electro-optical properties of molecular materials and the nature of low-lying exciton states. Molecular materials composed by oligoacenes are extensively investigated for their semiconducting and optoelectronic properties. Here, we analyze the exciton states derived from time-dependent density functional theory (TDDFT) calculations for two oligoacene model aggregates: naphthalene and anthracene dimers. To unravel the role of inter-molecular interactions, a set of diabatic states is selected, chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space including two occupied and two unoccupied orbitals for each molecular monomer. We study energy profiles and disentangle inter-state couplings to disclose the (CT) character of singlet and triplet exciton states and assess the influence of inter-molecular orientation by displacing one molecule with respect to the other along the longitudinal translation coordinate. The analysis shows that (CT) contributions are relevant, although comparably less effective for triplet excitons, and induce a non-negligible mixed character to the low-lying exciton states for eclipsed monomers and for small translational displacements. Such (CT) contributions govern the La/Lb state inversion occurring for the low-lying singlet exciton states of naphthalene dimer and contribute to the switch from H- to J-aggregate type of the strongly allowed Bb transition of both oligoacene aggregates. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | MDPI | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | |
dc.subject | oligoacenes | es_ES |
dc.subject | exciton states | es_ES |
dc.subject | singlet states | es_ES |
dc.subject | triplet states | es_ES |
dc.subject | TDDFT | es_ES |
dc.subject | diabatization | es_ES |
dc.subject | adiabatic states | es_ES |
dc.subject | diabatic states | es_ES |
dc.subject | frenkel excitons | es_ES |
dc.subject | charge resonance states | es_ES |
dc.subject | charge transfer states | es_ES |
dc.title | Intermolecular Interactions and Charge Resonance Contributions to Triplet and Singlet Exciton States of Oligoacene Aggregates | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.date.updated | 2023-01-06T13:52:48Z | |
dc.rights.holder | © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/ 4.0/). | es_ES |
dc.relation.publisherversion | https://www.mdpi.com/1420-3049/28/1/119 | es_ES |
dc.identifier.doi | 10.3390/molecules28010119 | |
dc.departamentoes | Polímeros y Materiales Avanzados: Física, Química y Tecnología | |
dc.departamentoeu | Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia |
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Except where otherwise noted, this item's license is described as © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/ 4.0/).