Author, as appears in the article.: Sousa, C; Sánchez-Mansilla, A; Broer, R; Straatsma, TP; de Graaf, C
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis / Sánchez Mansilla, Aitor María
Keywords: Charge-transfer states valence thin-films tetracene exciton fission exchange-energy electronic couplings dimers design approximation
Abstract: Perylenediimide molecules constitute a family of chromophores that undergo singlet fission, a process in which an excited singlet state converts into lower energy triplets on two neighboring molecules, potentially increasing the efficiency of organic solar cells. Here, the nonorthogonal configuration interaction method is applied to study the effect of the different crystal packing of various perylenediimide derivatives on the relative energies of the singlet and triplet states, the intermolecular electronic couplings, and the relative rates for singlet fission. The analysis of the wave functions and electronic couplings reveals that charge transfer states play an important role in the singlet fission mechanism. Dimer conformations where the PDI molecules are at large displacements along the long axis and short on the short axis are posed as the most favorable for singlet fission. The role of the substituent at the imide group has been inspected concluding that, although it has no effect in the energies, for some conformations it significantly influences the electronic couplings, and therefore, replacing this substituent with hydrogen may introduce artifacts in the computational modeling of the PDI molecules.
Thematic Areas: Química Physics, atomic, molecular & chemical Physical and theoretical chemistry Odontología Medicine (miscellaneous) Medicina ii Medicina i Materiais Interdisciplinar Geociências General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, physical Biotecnología Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: coen.degraaf@urv.cat aitor.sanchezm@estudiants.urv.cat
Author identifier: 0000-0001-8114-6658
Record's date: 2024-08-03
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/full/10.1021/acs.jpca.3c04975
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of Physical Chemistry a. 127 (47): 9944-9958
APA: Sousa, C; Sánchez-Mansilla, A; Broer, R; Straatsma, TP; de Graaf, C (2023). A Nonorthogonal Configuration Interaction Approach to Singlet Fission in Perylenediimide Compounds. Journal Of Physical Chemistry a, 127(47), 9944-9958. DOI: 10.1021/acs.jpca.3c04975
Article's DOI: 10.1021/acs.jpca.3c04975
Entity: Universitat Rovira i Virgili
Journal publication year: 2023
Publication Type: Journal Publications