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 »
- Authors:
-
- Technical Univ. of Denmark, Roskilde (Denmark)
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
- 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. doi: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}
}
Web of Science
Works referenced in this record:
Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics
journal, January 2013
- Lemke, Henrik T.; Bressler, Christian; Chen, Lin X.
- The Journal of Physical Chemistry A, Vol. 117, Issue 4
Matrix Organization and Merit Factor Evaluation as a Method to Address the Challenge of Finding a Polymer Material for Roll Coated Polymer Solar Cells
journal, February 2015
- Bundgaard, Eva; Livi, Francesco; Hagemann, Ole
- Advanced Energy Materials, Vol. 5, Issue 10
Photoinduced Charge Generation and Recombination Dynamics in Model Donor/Acceptor Pairs for Organic Solar Cell Applications: A Full Quantum-Chemical Treatment
journal, April 2005
- Lemaur, Vincent; Steel, Michelle; Beljonne, David
- Journal of the American Chemical Society, Vol. 127, Issue 16
X-ray free-electron lasers
journal, November 2010
- McNeil, Brian W. J.; Thompson, Neil R.
- Nature Photonics, Vol. 4, Issue 12
Concepts in x-ray physics
text, January 2009
- Santra, Robin
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Achieving few-femtosecond time-sorting at hard X-ray free-electron lasers
journal, February 2013
- Harmand, M.; Coffee, R.; Bionta, M. R.
- Nature Photonics, Vol. 7, Issue 3
Impulsive UV-pump/X-ray probe study of vibrational dynamics in glycine
journal, October 2018
- Mincigrucci, Riccardo; Kowalewski, Markus; Rouxel, Jérémy R.
- Scientific Reports, Vol. 8, Issue 1
Coherent structural trapping through wave packet dispersion during photoinduced spin state switching
journal, May 2017
- Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert
- Nature Communications, Vol. 8, Issue 1
Conformational and electronic properties of small benzothiadiazole-cored oligomers with aryl flanking units: Thiophene versus Furan
journal, January 2017
- Raychev, Deyan; Guskova, Olga; Seifert, Gotthard
- Computational Materials Science, Vol. 126
Infrared-laser-pulse-enhanced ultrafast fragmentation of following Auger decay: Mixed quantum-classical simulations
journal, December 2018
- Ganesa Subramanian, Murali Krishna; Santra, Robin; Welsch, Ralph
- Physical Review A, Vol. 98, Issue 6
Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source
journal, January 2017
- Pertot, Yoann; Schmidt, Cédric; Matthews, Mary
- Science, Vol. 355, Issue 6322
Ultrafast Dynamics of Photoionized Acetylene
journal, December 2011
- Madjet, Mohamed El-Amine; Vendrell, Oriol; Santra, Robin
- Physical Review Letters, Vol. 107, Issue 26
Ultrafast X-Ray Spectroscopy of Conical Intersections
journal, June 2018
- Neville, Simon P.; Chergui, Majed; Stolow, Albert
- Physical Review Letters, Vol. 120, Issue 24
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses
journal, March 2015
- Canton, Sophie E.; Kjær, Kasper S.; Vankó, György
- Nature Communications, Vol. 6, Issue 1
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005
- Glatzel, Pieter; Bergmann, Uwe
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
A computer simulation method for the calculation of equilibrium constants for the formation of physical clusters of molecules: Application to small water clusters
journal, January 1982
- Swope, William C.; Andersen, Hans C.; Berens, Peter H.
- The Journal of Chemical Physics, Vol. 76, Issue 1
Challenges in XUV Photochemistry Simulations: A Case Study on Ultrafast Fragmentation Dynamics of the Benzene Radical Cation
journal, January 2018
- Bazzi, Sophia; Welsch, Ralph; Vendrell, Oriol
- The Journal of Physical Chemistry A, Vol. 122, Issue 4
Models of charge pair generation in organic solar cells
journal, January 2015
- Few, Sheridan; Frost, Jarvist M.; Nelson, Jenny
- Physical Chemistry Chemical Physics, Vol. 17, Issue 4
Conjugated Polymer-Based Organic Solar Cells
journal, April 2007
- Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar
- Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338
Ultrafast strong-field dissociative ionization dynamics of CH2Br2 probed by femtosecond soft x-ray transient absorption spectroscopy
journal, May 2008
- Loh, Zhi-Heng; Leone, Stephen R.
- The Journal of Chemical Physics, Vol. 128, Issue 20
Infrared-laser-pulse-enhanced ultrafast fragmentation of $N_2^{2+}$ following Auger decay: Mixed quantum-classical simulations
text, January 2018
- Ganesa Subramanian, Murali Krishna; Santra, Robin; Welsch, Ralph
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2′-bipyridine)(CN) 4 ] 2−
journal, January 2018
- Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.
- Physical Chemistry Chemical Physics, Vol. 20, Issue 6
Beyond structure: ultrafast X-ray absorption spectroscopy as a probe of non-adiabatic wavepacket dynamics
journal, January 2016
- Neville, Simon P.; Averbukh, Vitali; Patchkovskii, Serguei
- Faraday Discussions, Vol. 194
Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption
journal, June 2017
- Wolf, T. J. A.; Myhre, R. H.; Cryan, J. P.
- Nature Communications, Vol. 8, Issue 1
Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics
journal, October 2016
- Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco
- The Journal of Chemical Physics, Vol. 145, Issue 14
Control of Local Ionization and Charge Transfer in the Bifunctional Molecule 2-Phenylethyl- N , N -dimethylamine Using Rydberg Fingerprint Spectroscopy
journal, March 2005
- Cheng, Wei; Kuthirummal, Narayanan; Gosselin, Jaimie L.
- The Journal of Physical Chemistry A, Vol. 109, Issue 9
Low band gap polymers for organic photovoltaics
journal, July 2007
- Bundgaard, Eva; Krebs, Frederik C.
- Solar Energy Materials and Solar Cells, Vol. 91, Issue 11, p. 954-985
Nonadiabatic Molecular Dynamics Based on Trajectories
journal, December 2013
- de Carvalho, Felipe; Bouduban, Marine; Curchod, Basile
- Entropy, Vol. 16, Issue 1
Polymer Solar Cells
journal, January 1991
- Zhuravleva, T. S.; Vannikov, A. V.
- Materials Science Forum, Vol. 21
Efficiency of bulk-heterojunction organic solar cells
journal, December 2013
- Scharber, M. C.; Sariciftci, N. S.
- Progress in Polymer Science, Vol. 38, Issue 12
Molecular Structural Dynamics Probed by Ultrafast X-Ray Absorption Spectroscopy
journal, March 2010
- Bressler, Christian; Chergui, Majed
- Annual Review of Physical Chemistry, Vol. 61, Issue 1
Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution
journal, September 2016
- Haldrup, Kristoffer; Dohn, Asmus O.; Shelby, Megan L.
- The Journal of Physical Chemistry A, Vol. 120, Issue 38
Femtosecond Time-Resolved Photoelectron Spectroscopy
journal, April 2004
- Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.
- Chemical Reviews, Vol. 104, Issue 4
State-resolved attosecond reversible and irreversible dynamics in strong optical fields
journal, February 2017
- Sabbar, Mazyar; Timmers, Henry; Chen, Yi-Jen
- Nature Physics, Vol. 13, Issue 5
Coupled perturbed Hartree—Fock equations. An alternative derivation and generalization to non-orthogonal orbitals
journal, March 1994
- Paizs, Béla; Mayer, István
- Chemical Physics Letters, Vol. 220, Issue 1-2
Conjugated Polymer-Based Organic Solar Cells
journal, July 2007
- Guenes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar
- ChemInform, Vol. 38, Issue 31
Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction
journal, April 2017
- Attar, Andrew R.; Bhattacherjee, Aditi; Pemmaraju, C. D.
- Science, Vol. 356, Issue 6333
Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions
journal, December 1995
- Yu, G.; Gao, J.; Hummelen, J. C.
- Science, Vol. 270, Issue 5243, p. 1789-1791
Polymer solar cells: Recent development and possible routes for improvement in the performance
journal, February 2010
- Cai, Wanzhu; Gong, Xiong; Cao, Yong
- Solar Energy Materials and Solar Cells, Vol. 94, Issue 2
Polymer solar cells
journal, February 2012
- Li, Gang; Zhu, Rui; Yang, Yang
- Nature Photonics, Vol. 6, Issue 3
Charge transfer relaxation in donor–acceptor type conjugated materials
journal, January 2013
- Scarongella, Mariateresa; Laktionov, Andrey; Rothlisberger, Ursula
- Journal of Materials Chemistry C, Vol. 1, Issue 12
Derivative studies in hartree-fock and møller-plesset theories
journal, March 1979
- Pople, J. A.; Krishnan, R.; Schlegel, H. B.
- International Journal of Quantum Chemistry, Vol. 16, Issue S13
Concepts in x-ray physics
journal, December 2008
- Santra, Robin
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 2
Ultrafast Dynamics of Photoionized Acetylene
text, January 2011
- Madjet, Mohamed El Amine; Vendrell Romagosa, Oriol; Santra, Robin
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Orbital-specific mapping of the ligand exchange dynamics of $Fe(CO)_{5}$ in solution
text, January 2015
- Wernet, Ph.; Kunnus, K.; Josefsson, I.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Force Constants and Dipole‐Moment Derivatives of Molecules from Perturbed Hartree–Fock Calculations. I
journal, August 1968
- Gerratt, J.; Mills, I. M.
- The Journal of Chemical Physics, Vol. 49, Issue 4
Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution
journal, April 2015
- Wernet, Ph.; Kunnus, K.; Josefsson, I.
- Nature, Vol. 520, Issue 7545
Synthesis and characterization of a thiophene-benzothiadiazole copolymer
journal, May 2009
- Li, Ji-Cheng; Kim, Se-Jung; Lee, Soo-Hyoung
- Macromolecular Research, Vol. 17, Issue 5
Recent experimental and theoretical developments in time-resolved X-ray spectroscopies
journal, October 2014
- Milne, C. J.; Penfold, T. J.; Chergui, M.
- Coordination Chemistry Reviews, Vol. 277-278
Molecular dynamics with electronic transitions
journal, July 1990
- Tully, John C.
- The Journal of Chemical Physics, Vol. 93, Issue 2
Concepts in x-ray physics
journal, July 2009
- Santra, R.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 16
Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL
journal, June 2017
- Obara, Yuki; Ito, Hironori; Ito, Terumasa
- Structural Dynamics, Vol. 4, Issue 4
Probing wavepacket dynamics using ultrafast x-ray spectroscopy
journal, September 2015
- Capano, G.; Milne, C. J.; Chergui, M.
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 48, Issue 21
Core-level transient absorption spectroscopy as a probe of electron hole relaxation in photoionized H + (H 2 O) n
journal, January 2014
- Li, Zheng; El-Amine Madjet, Mohamed; Vendrell, Oriol
- Faraday Discuss., Vol. 171
Femtosecond Time-Resolved Photoelectron Spectroscopy
journal, June 2004
- Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.
- ChemInform, Vol. 35, Issue 24
Time-resolved X-ray absorption spectroscopy with a water-window high-harmonic source
conference, June 2017
- Pertot, Yoann; Schmidt, Cedric; Matthews, Mary
- 2017 Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC)
Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity
text, January 2015
- Hao, Yajiang; Inhester, Ludger; Hanasaki, Kota
- arXiv
Ultrafast X-ray spectroscopy of conical intersections
text, January 2018
- Neville, Simon P.; Chergui, Majed; Stolow, Albert
- arXiv
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
Simulation of time-resolved x-ray absorption spectroscopy of ultrafast dynamics in particle-hole-excited 4‐(2-thienyl)-2,1,3-benzothiadiazole
text, January 2020
- Khalili, Khadijeh; Inhester, Ludger; Arnold, Caroline
- Deutsches Elektronen-Synchrotron, DESY, Hamburg