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Title: Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy

Abstract

Theoretical and experimental methodologies that can characterize electronic and nuclear dynamics, and the coupling between the two, are needed to understand photoinduced charge transfer in molecular building blocks used in organic photovoltaics. Ongoing developments in ultrafast pump-probe techniques such as time-resolved X-ray absorption spectroscopy, using an X-ray free electron laser in combination with an ultraviolet femtosecond laser, present desirable probes of coupled electronic and nuclear dynamics. In this work, we investigate the charge transfer dynamics of a donor-acceptor pair, which is widely used as a building block in low bandgap block copolymers for organic photovoltaics. We simulate the dynamics of the benzothiadiazole-thiophene molecule upon photoionization with a vacuum ultraviolet (VUV) pulse and study the potential of probing the subsequent charge dynamics using time-resolved X-ray absorption spectroscopy. The photoinduced dynamics are calculated using on-the-fly nonadiabatic molecular dynamics simulations based on Tully's Fewest Switches Surface Hopping approach. We calculate the X-ray absorption spectrum as a function of time after ionization at the Hartree-Fock level. The changes in the time-resolved X-ray absorption spectrum at the sulfur K-edge reveal the ultrafast charge carrier dynamics in the molecule occurring on a femtosecond time scale. These theoretical findings anticipate that ultrafast time-resolved X-ray absorption spectroscopy usingmore » an X-ray probe in combination with a VUV pump offers a new approach to investigate the detailed dynamics of organic photovoltaic materials.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Technical Univ. of Denmark, Roskilde (Denmark)
  2. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
  3. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); Univ. of Hamburg (Germany)
Publication Date:
Research Org.:
Kansas State Univ., Manhattan, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1613239
Alternate Identifier(s):
OSTI ID: 1544455
Grant/Contract Number:  
SC0019451
Resource Type:
Accepted Manuscript
Journal Name:
Structural Dynamics
Additional Journal Information:
Journal Volume: 6; Journal Issue: 4; Journal ID: ISSN 2329-7778
Publisher:
American Crystallographic Association/AIP
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; Physics

Citation Formats

Khalili, Khadijeh, Inhester, Ludger, Arnold, Caroline, Welsch, Ralph, Andreasen, Jens Wenzel, and Santra, Robin. Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5097653.
Khalili, Khadijeh, Inhester, Ludger, Arnold, Caroline, Welsch, Ralph, Andreasen, Jens Wenzel, & Santra, Robin. Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy. United States. https://doi.org/10.1063/1.5097653
Khalili, Khadijeh, Inhester, Ludger, Arnold, Caroline, Welsch, Ralph, Andreasen, Jens Wenzel, and Santra, Robin. Tue . "Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy". United States. https://doi.org/10.1063/1.5097653. https://www.osti.gov/servlets/purl/1613239.
@article{osti_1613239,
title = {Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy},
author = {Khalili, Khadijeh and Inhester, Ludger and Arnold, Caroline and Welsch, Ralph and Andreasen, Jens Wenzel and Santra, Robin},
abstractNote = {Theoretical and experimental methodologies that can characterize electronic and nuclear dynamics, and the coupling between the two, are needed to understand photoinduced charge transfer in molecular building blocks used in organic photovoltaics. Ongoing developments in ultrafast pump-probe techniques such as time-resolved X-ray absorption spectroscopy, using an X-ray free electron laser in combination with an ultraviolet femtosecond laser, present desirable probes of coupled electronic and nuclear dynamics. In this work, we investigate the charge transfer dynamics of a donor-acceptor pair, which is widely used as a building block in low bandgap block copolymers for organic photovoltaics. We simulate the dynamics of the benzothiadiazole-thiophene molecule upon photoionization with a vacuum ultraviolet (VUV) pulse and study the potential of probing the subsequent charge dynamics using time-resolved X-ray absorption spectroscopy. The photoinduced dynamics are calculated using on-the-fly nonadiabatic molecular dynamics simulations based on Tully's Fewest Switches Surface Hopping approach. We calculate the X-ray absorption spectrum as a function of time after ionization at the Hartree-Fock level. The changes in the time-resolved X-ray absorption spectrum at the sulfur K-edge reveal the ultrafast charge carrier dynamics in the molecule occurring on a femtosecond time scale. These theoretical findings anticipate that ultrafast time-resolved X-ray absorption spectroscopy using an X-ray probe in combination with a VUV pump offers a new approach to investigate the detailed dynamics of organic photovoltaic materials.},
doi = {10.1063/1.5097653},
journal = {Structural Dynamics},
number = 4,
volume = 6,
place = {United States},
year = {2019},
month = {7}
}

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    Works referencing / citing this record:

    Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole
    journal, July 2020

    • Khalili, Khadijeh; Inhester, Ludger; Arnold, Caroline
    • Structural Dynamics, Vol. 7, Issue 4
    • DOI: 10.1063/4.0000016

    Hole dynamics in a photovoltaic donor-acceptor couple revealed by simulated time-resolved X-ray absorption spectroscopy
    text, January 2019

    • Khalili, Khadijeh; Inhester, Ludger; Arnold, Caroline
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2019-02799