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Cluster-Based Approach Utilizing Optimally Tuned TD-DFT to Calculate Absorption Spectra of Organic Semiconductor Thin Films
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    Cluster-Based Approach Utilizing Optimally Tuned TD-DFT to Calculate Absorption Spectra of Organic Semiconductor Thin Films
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 24, 9369–9387
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    https://doi.org/10.1021/acs.jctc.3c01107
    Published December 10, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    The photophysics of organic semiconductor (OSC) thin films or crystals has garnered significant attention in recent years since a comprehensive theoretical understanding of the various processes occurring upon photoexcitation is crucial for assessing the efficiency of OSC materials. To date, research in this area has relied on methods using Frenkel–Holstein Hamiltonians, calculations of the GW-Bethe–Salpeter equation with periodic boundaries, or cluster-based approaches using quantum chemical methods, with each of the three approaches having distinct advantages and disadvantages. In this work, we introduce an optimally tuned, range-separated time-dependent density functional theory approach to accurately reproduce the total and polarization-resolved absorption spectra of pentacene, tetracene, and perylene thin films, all representative OSC materials. Our approach achieves excellent agreement with experimental data (mostly ≤0.1 eV) when combined with the utilization of clusters comprising multiple monomers and a standard polarizable continuum model to simulate the thin-film environment. Our protocol therefore addresses a major drawback of cluster-based approaches and makes them attractive tools for OSC investigations. Its key advantages include its independence from external, system-specific fitting parameters and its straightforward application with well-known quantum chemical program codes. It demonstrates how chemical intuition can help to reduce computational cost and still arrive at chemically meaningful and almost quantitative results.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.3c01107.

    • Overview of previous studies on OSC thin films, more details on selected monomer calculations and geometries, excited states’ characterization, spectra of all clusters mentioned, and Cartesian coordinates of all structures (PDF)

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    Cited By

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    This article is cited by 4 publications.

    1. Frederik Unger, Daniel Lepple, Maximilian Asbach, Luca Craciunescu, Clemens Zeiser, Andreas F. Kandolf, Zbyněk Fišer, Jakub Hagara, Jan Hagenlocher, Stefan Hiller, Sara Haug, Marian Deutsch, Peter Grüninger, Jiří Novák, Holger F. Bettinger, Katharina Broch, Bernd Engels, Frank Schreiber. Optical Absorption Properties in Pentacene/Tetracene Solid Solutions. The Journal of Physical Chemistry A 2024, 128 (4) , 747-760. https://doi.org/10.1021/acs.jpca.3c06737
    2. Sebastian Hammer, Tristan L. Britt, Laurenz Kremeyer, Maximilian Rödel, David Cai, Jens Pflaum, Bradley J. Siwick. Excimer formation in zinc-phthalocyanine revealed using ultrafast electron diffraction. Proceedings of the National Academy of Sciences 2024, 121 (51) https://doi.org/10.1073/pnas.2411975121
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    4. Jin Zhang, Alejandra Traspas Muiña, Duncan V Mifsud, Zuzana Kaňuchová, Klaudia Cielinska, Péter Herczku, K K Rahul, Sándor T S Kovács, Richárd Rácz, Julia C Santos, Alfred T Hopkinson, Luca Craciunescu, Nykola C Jones, Søren V Hoffmann, Sándor Biri, István Vajda, István Rajta, Anita Dawes, Bhalamurugan Sivaraman, Zoltán Juhász, Béla Sulik, Harold Linnartz, Liv Hornekær, Felipe Fantuzzi, Nigel J Mason, Sergio Ioppolo. A systematic IR and VUV spectroscopic investigation of ion, electron, and thermally processed ethanolamine ice. Monthly Notices of the Royal Astronomical Society 2024, 533 (1) , 826-840. https://doi.org/10.1093/mnras/stae1860

    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2023, 19, 24, 9369–9387
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.3c01107
    Published December 10, 2023
    Copyright © 2023 American Chemical Society

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