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Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles

[Image: see text] The ultrafast dynamics of charge carriers in organic donor–acceptor interfaces are of primary importance to understanding the fundamental properties of these systems. In this work, we focus on a charge-transfer complex formed by quaterthiophene p-doped by tetrafluoro-tetracyanoquin...

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Autores principales: Jacobs, Matheus, Krumland, Jannis, Valencia, Ana M., Cocchi, Caterina
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10614200/
https://www.ncbi.nlm.nih.gov/pubmed/37824697
http://dx.doi.org/10.1021/acs.jpca.3c03709
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author Jacobs, Matheus
Krumland, Jannis
Valencia, Ana M.
Cocchi, Caterina
author_facet Jacobs, Matheus
Krumland, Jannis
Valencia, Ana M.
Cocchi, Caterina
author_sort Jacobs, Matheus
collection PubMed
description [Image: see text] The ultrafast dynamics of charge carriers in organic donor–acceptor interfaces are of primary importance to understanding the fundamental properties of these systems. In this work, we focus on a charge-transfer complex formed by quaterthiophene p-doped by tetrafluoro-tetracyanoquinodimethane and investigate electron dynamics and vibronic interactions also at finite temperatures by applying a femtosecond pulse in resonance with the two lowest energy excitations of the system with perpendicular and parallel polarization with respect to the interface. The adopted ab initio formalism based on real-time time-dependent density-functional theory coupled to Ehrenfest dynamics enables monitoring the dynamical charge transfer across the interface and assessing the role played by the nuclear motion. Our results show that the strong intermolecular interactions binding the complex already in the ground state influence the dynamics, too. The analysis of the nuclear motion involved in these processes reveals the participation of different vibrational modes depending on the electronic states stimulated by the resonant pulse. Coupled donor–acceptor modes mostly influence the excited state polarized across the interface, while intramolecular vibrations in the donor molecule dominate the excitation in the orthogonal direction. The results obtained at finite temperatures are overall consistent with this picture, although thermal disorder contributes to slightly decreasing interfacial charge transfer.
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spelling pubmed-106142002023-10-31 Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles Jacobs, Matheus Krumland, Jannis Valencia, Ana M. Cocchi, Caterina J Phys Chem A [Image: see text] The ultrafast dynamics of charge carriers in organic donor–acceptor interfaces are of primary importance to understanding the fundamental properties of these systems. In this work, we focus on a charge-transfer complex formed by quaterthiophene p-doped by tetrafluoro-tetracyanoquinodimethane and investigate electron dynamics and vibronic interactions also at finite temperatures by applying a femtosecond pulse in resonance with the two lowest energy excitations of the system with perpendicular and parallel polarization with respect to the interface. The adopted ab initio formalism based on real-time time-dependent density-functional theory coupled to Ehrenfest dynamics enables monitoring the dynamical charge transfer across the interface and assessing the role played by the nuclear motion. Our results show that the strong intermolecular interactions binding the complex already in the ground state influence the dynamics, too. The analysis of the nuclear motion involved in these processes reveals the participation of different vibrational modes depending on the electronic states stimulated by the resonant pulse. Coupled donor–acceptor modes mostly influence the excited state polarized across the interface, while intramolecular vibrations in the donor molecule dominate the excitation in the orthogonal direction. The results obtained at finite temperatures are overall consistent with this picture, although thermal disorder contributes to slightly decreasing interfacial charge transfer. American Chemical Society 2023-10-12 /pmc/articles/PMC10614200/ /pubmed/37824697 http://dx.doi.org/10.1021/acs.jpca.3c03709 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Jacobs, Matheus
Krumland, Jannis
Valencia, Ana M.
Cocchi, Caterina
Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title_full Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title_fullStr Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title_full_unstemmed Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title_short Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles
title_sort pulse-induced dynamics of a charge-transfer complex from first principles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10614200/
https://www.ncbi.nlm.nih.gov/pubmed/37824697
http://dx.doi.org/10.1021/acs.jpca.3c03709
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