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Multiscale modeling of structural disorder and environmental effects on the ground and excited states properties of a conjugated donor-acceptor polymer in the bulk phase

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Title: Multiscale modeling of structural disorder and environmental effects on the ground and excited states properties of a conjugated donor-acceptor polymer in the bulk phase
Authors: Rezende Franco, Leandro, 1989, Valverde, Danillo, Marchiori, Cleber F.N., Moons, Ellen, Wang, Ergang, 1981, Araujo, C. Moyses
Source: JPhys Energy. 7(4)
Subject Terms: structural disorder, multiscale simulation, donor-acceptor polymers for organic photovoltaics, fundamental gap renormalization, sequential QM/MM, charge transfer excited states, solution processed thin films
Description: We herein undertook a multiscale approach combining molecular dynamics (MD) simulations of solution-processed polymer bulk with sequential quantum mechanics/molecular mechanics (s-QM/MM) calculations to assess the influence of structural disorder and environmental effects on the electronic structure of conjugated donor-acceptor (D-A) polymers in bulk phase. As a case study, PF5-Y5 polymer bulk formation is modeled via gradual solvent removal under ambient conditions. The electronic structure is analyzed using state-of-the-art electronic structure methods, including optimally tuned range-separated hybrids (OT-DFT), double-hybrid functionals, and the second order algebraic diagrammatic construction (ADC(2)) method as a reference. Environmental effects are accounted for using both implicit and explicit electrostatic embedding models. Our findings reveal that structural disorder at the D-A interfaces reduces frontier orbital overlap and narrows the fundamental gap by localizing the orbitals, primarily due to significant LUMO stabilization on the acceptor unit. This effect enhances the charge-transfer (CT) character of low-lying singlet and triplet states within the OT-DFT approach, while double hybrid methods preserve a more localized nature. Disorder reshapes the energetic gaps between singlet-singlet and singlet-triplet excited states and increases its energetic disorder, with CT-rich states being particularly sensitive. Explicit electrostatic embedding further amplifies CT character and disorder in singlets while preserving triplet localization. These effects contribute to spectral broadening and help explain a shoulder feature in the visible region, linking it to structural disorder and ambient anisotropy alongside CT excitations. The choice of QM method and environment treatment in QM/MM simulations is critical, neglecting anisotropy in the surroundings can influence the excited-state descriptions in D-A materials. This work advances our theoretical understanding of organic photovoltaics by highlighting these interrelated effects.
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  Label: Title
  Group: Ti
  Data: Multiscale modeling of structural disorder and environmental effects on the ground and excited states properties of a conjugated donor-acceptor polymer in the bulk phase
– Name: Author
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  Data: <searchLink fieldCode="AR" term="%22Rezende+Franco%2C+Leandro%22">Rezende Franco, Leandro</searchLink>, 1989<br /><searchLink fieldCode="AR" term="%22Valverde%2C+Danillo%22">Valverde, Danillo</searchLink><br /><searchLink fieldCode="AR" term="%22Marchiori%2C+Cleber+F%2EN%2E%22">Marchiori, Cleber F.N.</searchLink><br /><searchLink fieldCode="AR" term="%22Moons%2C+Ellen%22">Moons, Ellen</searchLink><br /><searchLink fieldCode="AR" term="%22Wang%2C+Ergang%22">Wang, Ergang</searchLink>, 1981<br /><searchLink fieldCode="AR" term="%22Araujo%2C+C%2E+Moyses%22">Araujo, C. Moyses</searchLink>
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  Label: Source
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  Data: <i>JPhys Energy</i>. 7(4)
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  Data: <searchLink fieldCode="DE" term="%22structural+disorder%22">structural disorder</searchLink><br /><searchLink fieldCode="DE" term="%22multiscale+simulation%22">multiscale simulation</searchLink><br /><searchLink fieldCode="DE" term="%22donor-acceptor+polymers+for+organic+photovoltaics%22">donor-acceptor polymers for organic photovoltaics</searchLink><br /><searchLink fieldCode="DE" term="%22fundamental+gap+renormalization%22">fundamental gap renormalization</searchLink><br /><searchLink fieldCode="DE" term="%22sequential+QM%2FMM%22">sequential QM/MM</searchLink><br /><searchLink fieldCode="DE" term="%22charge+transfer+excited+states%22">charge transfer excited states</searchLink><br /><searchLink fieldCode="DE" term="%22solution+processed+thin+films%22">solution processed thin films</searchLink>
– Name: Abstract
  Label: Description
  Group: Ab
  Data: We herein undertook a multiscale approach combining molecular dynamics (MD) simulations of solution-processed polymer bulk with sequential quantum mechanics/molecular mechanics (s-QM/MM) calculations to assess the influence of structural disorder and environmental effects on the electronic structure of conjugated donor-acceptor (D-A) polymers in bulk phase. As a case study, PF5-Y5 polymer bulk formation is modeled via gradual solvent removal under ambient conditions. The electronic structure is analyzed using state-of-the-art electronic structure methods, including optimally tuned range-separated hybrids (OT-DFT), double-hybrid functionals, and the second order algebraic diagrammatic construction (ADC(2)) method as a reference. Environmental effects are accounted for using both implicit and explicit electrostatic embedding models. Our findings reveal that structural disorder at the D-A interfaces reduces frontier orbital overlap and narrows the fundamental gap by localizing the orbitals, primarily due to significant LUMO stabilization on the acceptor unit. This effect enhances the charge-transfer (CT) character of low-lying singlet and triplet states within the OT-DFT approach, while double hybrid methods preserve a more localized nature. Disorder reshapes the energetic gaps between singlet-singlet and singlet-triplet excited states and increases its energetic disorder, with CT-rich states being particularly sensitive. Explicit electrostatic embedding further amplifies CT character and disorder in singlets while preserving triplet localization. These effects contribute to spectral broadening and help explain a shoulder feature in the visible region, linking it to structural disorder and ambient anisotropy alongside CT excitations. The choice of QM method and environment treatment in QM/MM simulations is critical, neglecting anisotropy in the surroundings can influence the excited-state descriptions in D-A materials. This work advances our theoretical understanding of organic photovoltaics by highlighting these interrelated effects.
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        Value: 10.1088/2515-7655/adeae7
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      – Text: English
    Subjects:
      – SubjectFull: structural disorder
        Type: general
      – SubjectFull: multiscale simulation
        Type: general
      – SubjectFull: donor-acceptor polymers for organic photovoltaics
        Type: general
      – SubjectFull: fundamental gap renormalization
        Type: general
      – SubjectFull: sequential QM/MM
        Type: general
      – SubjectFull: charge transfer excited states
        Type: general
      – SubjectFull: solution processed thin films
        Type: general
    Titles:
      – TitleFull: Multiscale modeling of structural disorder and environmental effects on the ground and excited states properties of a conjugated donor-acceptor polymer in the bulk phase
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            NameFull: Rezende Franco, Leandro
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            NameFull: Valverde, Danillo
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            NameFull: Marchiori, Cleber F.N.
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            NameFull: Moons, Ellen
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            NameFull: Wang, Ergang
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            NameFull: Araujo, C. Moyses
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            – D: 01
              M: 01
              Type: published
              Y: 2025
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            – TitleFull: JPhys Energy
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