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Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole
To date, alternating co-polymers based on electron-rich and electron-poor units are the most attractive materials to control functionality of organic semiconductor layers in which ultrafast excited-state processes play a key role. We present a computational study of the photoinduced excited-state dy...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Crystallographic Association
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7340508/ https://www.ncbi.nlm.nih.gov/pubmed/32665964 http://dx.doi.org/10.1063/4.0000016 |
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author | Khalili, Khadijeh Inhester, Ludger Arnold, Caroline Gertsen, Anders S. Andreasen, Jens Wenzel Santra, Robin |
author_facet | Khalili, Khadijeh Inhester, Ludger Arnold, Caroline Gertsen, Anders S. Andreasen, Jens Wenzel Santra, Robin |
author_sort | Khalili, Khadijeh |
collection | PubMed |
description | To date, alternating co-polymers based on electron-rich and electron-poor units are the most attractive materials to control functionality of organic semiconductor layers in which ultrafast excited-state processes play a key role. We present a computational study of the photoinduced excited-state dynamics of the 4-(2-thienyl)-2,1,3-benzothiadiazole (BT-1T) molecule, which is a common building block in the backbone of π-conjugated polymers used for organic electronics. In contrast to homo-polymer materials, such as oligothiophene, BT-1T has two non-identical units, namely, thiophene and benzothiadiazole, making it attractive for intramolecular charge transfer studies. To gain a thorough understanding of the coupling of excited-state dynamics with nuclear motion, we consider a scenario based on femtosecond time-resolved x-ray absorption spectroscopy using an x-ray free-electron laser in combination with a synchronized ultraviolet femtosecond laser. Using Tully's fewest switches surface hopping approach in combination with excited-state calculations at the level of configuration interaction singles, we calculate the gas-phase x-ray absorption spectrum at the carbon and nitrogen K edges as a function of time after excitation to the lowest electronically excited state. The results of our time-resolved calculations exhibit the charge transfer driven by non-Born-Oppenheimer physics from the benzothiadiazole to thiophene units during relaxation to the ground state. Furthermore, our ab initio molecular dynamics simulations indicate that the excited-state relaxation processes involve bond elongation in the benzothiadiazole unit as well as thiophene ring puckering at a time scale of 100 fs. We show that these dynamical trends can be identified from the time-dependent x-ray absorption spectrum. |
format | Online Article Text |
id | pubmed-7340508 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Crystallographic Association |
record_format | MEDLINE/PubMed |
spelling | pubmed-73405082020-07-13 Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole Khalili, Khadijeh Inhester, Ludger Arnold, Caroline Gertsen, Anders S. Andreasen, Jens Wenzel Santra, Robin Struct Dyn ARTICLES To date, alternating co-polymers based on electron-rich and electron-poor units are the most attractive materials to control functionality of organic semiconductor layers in which ultrafast excited-state processes play a key role. We present a computational study of the photoinduced excited-state dynamics of the 4-(2-thienyl)-2,1,3-benzothiadiazole (BT-1T) molecule, which is a common building block in the backbone of π-conjugated polymers used for organic electronics. In contrast to homo-polymer materials, such as oligothiophene, BT-1T has two non-identical units, namely, thiophene and benzothiadiazole, making it attractive for intramolecular charge transfer studies. To gain a thorough understanding of the coupling of excited-state dynamics with nuclear motion, we consider a scenario based on femtosecond time-resolved x-ray absorption spectroscopy using an x-ray free-electron laser in combination with a synchronized ultraviolet femtosecond laser. Using Tully's fewest switches surface hopping approach in combination with excited-state calculations at the level of configuration interaction singles, we calculate the gas-phase x-ray absorption spectrum at the carbon and nitrogen K edges as a function of time after excitation to the lowest electronically excited state. The results of our time-resolved calculations exhibit the charge transfer driven by non-Born-Oppenheimer physics from the benzothiadiazole to thiophene units during relaxation to the ground state. Furthermore, our ab initio molecular dynamics simulations indicate that the excited-state relaxation processes involve bond elongation in the benzothiadiazole unit as well as thiophene ring puckering at a time scale of 100 fs. We show that these dynamical trends can be identified from the time-dependent x-ray absorption spectrum. American Crystallographic Association 2020-07-06 /pmc/articles/PMC7340508/ /pubmed/32665964 http://dx.doi.org/10.1063/4.0000016 Text en © 2020 Author(s). 2329-7778/2020/7(4)/044101/9 All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | ARTICLES Khalili, Khadijeh Inhester, Ludger Arnold, Caroline Gertsen, Anders S. Andreasen, Jens Wenzel Santra, Robin Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title | Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title_full | Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title_fullStr | Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title_full_unstemmed | Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title_short | Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
title_sort | simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole |
topic | ARTICLES |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7340508/ https://www.ncbi.nlm.nih.gov/pubmed/32665964 http://dx.doi.org/10.1063/4.0000016 |
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