Articles producció científica> Química Física i Inorgànica

A Nonorthogonal Configuration Interaction Approach to Singlet Fission in Perylenediimide Compounds

  • Identification data

    Identifier: imarina:9332031
    Authors:
    Sousa, CSánchez-Mansilla, ABroer, RStraatsma, TPde Graaf, C
    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.
  • Others:

    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
  • Keywords:

    Chemistry, Physical,Medicine (Miscellaneous),Physical and Theoretical Chemistry,Physics, Atomic, Molecular & Chemical
    Charge-transfer states
    valence
    thin-films
    tetracene
    exciton fission
    exchange-energy
    electronic couplings
    dimers
    design
    approximation
    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
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