Direct observation of ultrafast symmetry reduction during internal conversion of 2-thiouracil using Coulomb explosion imaging

Jahnke, Till; Mai, Sebastian; Bhattacharyya, Surjendu; Chen, Keyu; Boll, Rebecca; Castellani, Maria Elena; Dold, Simon; Frühling, Ulrike; Green, Alice E.; Ilchen, Markus; Ingle, Rebecca; Kastirke, Gregor; Lam, Huynh Van Sa; Lever, Fabiano; Mayer, Dennis; Mazza, Tommaso; Mullins, Terence; Ovcharenko, Yevheniy; Senfftleben, Björn; Trinter, Florian; Tul-Noor, Atia; Usenko, Sergey; Venkatachalam, Anbu Selvam; Rudenko, Artem; Rolles, Daniel; Meyer, Michael; Ibrahim, Heide; Gühr, Markus

doi:10.1038/s41467-025-57083-3

Title: Direct observation of ultrafast symmetry reduction during internal conversion of 2-thiouracil using Coulomb explosion imaging

Journal Article · Fri Feb 28 00:00:00 UTC 2025 · Nature Communications

DOI: https://doi.org/10.1038/s41467-025-57083-3 · OSTI ID:3003063

^[1];

^[2]; Bhattacharyya, Surjendu ^[3];

^[3];

^[4]; Castellani, Maria Elena ^[5];

^[4]; Frühling, Ulrike ^[6];

^[7]; Ilchen, Markus ^[8];

^[9]; Kastirke, Gregor ^[10];

^[3]; Lever, Fabiano ^[6]; Mayer, Dennis ^[6];

^[4];

^[11] more »

Max-Planck-Institut für Kernphysik, Heidelberg (Germany); European XFEL, Schenefeld (Germany)
University of Vienna (Austria)
Kansas State University, Manhattan, KS (United States)
European XFEL, Schenefeld (Germany)
IRCCS Azienda Ospedaliero-Universitaria di Bologna (Italy)
Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
European XFEL, Schenefeld (Germany); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
European XFEL, Schenefeld (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Universität Hamburg (Germany)
University College London (United Kingdom)
Goethe-Universität Frankfurt (Germany)
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany)
Matériaux et Télécommunications, Québec (Canada); University of Ottawa, ON (Canada)
Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Universität Hamburg (Germany)

The photochemistry of heterocyclic molecules plays a decisive role for processes and applications like DNA photo-protection from UV damage and organic photocatalysis. The photochemical reactivity of heterocycles is determined by the redistribution of photoenergy into electronic and nuclear degrees of freedom, initially involving ultrafast internal conversion. Most heterocycles are planar in their ground state and internal conversion requires symmetry breaking. To lower the symmetry, the molecule must undergo an out-of-plane motion, which has not yet been observed directly. Here we show using the example of 2-thiouracil, how Coulomb explosion imaging can be utilized to extract comprehensive information on this molecular deformation, linking the extracted deplanarization of the molecular geometry to the previously studied temporal evolution of its electronic properties. Particularly, the protons of the exploded molecule are well-suited messengers carrying rich information on its geometry at distinct times after electronic excitation. We expect that our new analysis approach centered on these peripheral protons can be adapted as a general concept for future time-resolved studies of complex molecules in the gas phase.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Kansas State University, Manhattan, KS (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Deutsche Forschungsgemeinschaft; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-86ER13491; SC0020276

OSTI ID:: 3003063

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723

Publisher:: Springer Science and Business Media LLCCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Cold Target Recoil Ion Momentum Spectroscopy: a ‘momentum microscope’ to view atomic collision dynamics Dörner, R.; Mergel, V.; Jagutzki, O. Physics Reports, Vol. 330, Issue 2-3 https://doi.org/10.1016/S0370-1573(99)00109-X	journal	June 2000
Deformation, nuclear motion and fragmentation of core-excited CO2 probed by multiple-ion coincidence momentum imaging Saito, N.; Muramatsu, Y.; Chiba, H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 141, Issue 2-3 https://doi.org/10.1016/j.elspec.2004.06.007	journal	December 2004
Multicoincidence studies of photo and Auger electrons from fixed-in-space molecules using the COLTRIMS technique Jahnke, T.; Weber, Th.; Osipov, T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 141, Issue 2-3 https://doi.org/10.1016/j.elspec.2004.06.010	journal	December 2004
Coulomb imaging of the concerted and stepwise break up processes of OCS ions in intense femtosecond laser radiation Wales, Benji; Bisson, Éric; Karimi, Reza Journal of Electron Spectroscopy and Related Phenomena, Vol. 195 https://doi.org/10.1016/j.elspec.2014.05.003	journal	August 2014
Multiple ionization and Coulomb explosion of molecules, molecular complexes, clusters and solid surfaces Yatsuhashi, Tomoyuki; Nakashima, Nobuaki Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 34 https://doi.org/10.1016/j.jphotochemrev.2017.12.001	journal	March 2018
Intersystem Crossing Pathways in the Noncanonical Nucleobase 2-Thiouracil: A Time-Dependent Picture Mai, Sebastian; Marquetand, Philipp; González, Leticia The Journal of Physical Chemistry Letters, Vol. 7, Issue 11 https://doi.org/10.1021/acs.jpclett.6b00616	journal	May 2016
Triplet state. Its radiative and nonradiative properties El-Sayed, Mostafa A. Accounts of Chemical Research, Vol. 1, Issue 1 https://doi.org/10.1021/ar50001a002	journal	January 1968
The Ultraviolet Absorption Spectra of Thiouracils¹ Elion, Gertrude B.; Ide, Walter S.; Hitchings, George H. Journal of the American Chemical Society, Vol. 68, Issue 11 https://doi.org/10.1021/ja01215a004	journal	November 1946
Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction Figueira Nunes, Joao Pedro; Ibele, Lea Maria; Pathak, Shashank Journal of the American Chemical Society, Vol. 146, Issue 6 https://doi.org/10.1021/jacs.3c13046	journal	February 2024
The origin of efficient triplet state population in sulfur-substituted nucleobases Mai, Sebastian; Pollum, Marvin; Martínez-Fernández, Lara Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13077	journal	October 2016
Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation Ibrahim, Heide; Wales, Benji; Beaulieu, Samuel Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5422	journal	July 2014
Ultrafast isomerization initiated by X-ray core ionization Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9199	journal	September 2015
A metal-free polymeric photocatalyst for hydrogen production from water under visible light Wang, Xinchen; Maeda, Kazuhiko; Thomas, Arne Nature Materials, Vol. 8, Issue 1 https://doi.org/10.1038/nmat2317	journal	November 2008
Photo-cross-linking and high-resolution mass spectrometry for assignment of RNA-binding sites in RNA-binding proteins Kramer, Katharina; Sachsenberg, Timo; Beckmann, Benedikt M. Nature Methods, Vol. 11, Issue 10 https://doi.org/10.1038/nmeth.3092	journal	August 2014
Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy Mayer, D.; Lever, F.; Picconi, D. Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-021-27908-y	journal	January 2022
X-ray multiphoton-induced Coulomb explosion images complex single molecules Boll, Rebecca; Schäfer, Julia M.; Richard, Benoît Nature Physics, Vol. 18, Issue 4 https://doi.org/10.1038/s41567-022-01507-0	journal	February 2022
A ‘bottom up’, ab initio computational approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs Marchetti, Barbara; Karsili, Tolga N. V.; Ashfold, Michael N. R. Physical Chemistry Chemical Physics, Vol. 18, Issue 30 https://doi.org/10.1039/C6CP00165C	journal	January 2016
Ultrafast Coulomb explosion of a diiodomethane molecule induced by an X-ray free-electron laser pulse Takanashi, Tsukasa; Nakamura, Kosuke; Kukk, Edwin Physical Chemistry Chemical Physics, Vol. 19, Issue 30 https://doi.org/10.1039/C7CP01669G	journal	January 2017
Excited-state hydrogen detachment and hydrogen transfer driven by repulsive 1πσ* states: A new paradigm for nonradiative decay in aromatic biomolecules Sobolewski, A. L.; Domcke, W.; Dedonder-Lardeux, C. Physical Chemistry Chemical Physics, Vol. 4, Issue 7 https://doi.org/10.1039/b110941n	journal	February 2002
A combined experimental and theoretical study on realizing and using laser controlled torsion of molecules Madsen, C. B.; Madsen, L. B.; Viftrup, S. S. The Journal of Chemical Physics, Vol. 130, Issue 23 https://doi.org/10.1063/1.3149789	journal	June 2009
State-specific heavy-atom effect on intersystem crossing processes in 2-thiothymine: A potential photodynamic therapy photosensitizer Cui, Ganglong; Fang, Wei-hai The Journal of Chemical Physics, Vol. 138, Issue 4 https://doi.org/10.1063/1.4776261	journal	January 2013
Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp The Journal of Chemical Physics, Vol. 144, Issue 7 https://doi.org/10.1063/1.4941948	journal	February 2016
Surface hopping dynamics including intersystem crossing using the algebraic diagrammatic construction method Mai, Sebastian; Plasser, Felix; Pabst, Mathias The Journal of Chemical Physics, Vol. 147, Issue 18 https://doi.org/10.1063/1.4999687	journal	November 2017
Competition between ring-puckering and ring-opening excited state reactions exemplified on 5H-furan-2-one and derivatives Schalk, Oliver; Galiana, Joachim; Geng, Ting The Journal of Chemical Physics, Vol. 152, Issue 6 https://doi.org/10.1063/1.5129366	journal	February 2020
A comparative review of time-resolved x-ray and electron scattering to probe structural dynamics Lee, Yunbeom; Oang, Key Young; Kim, Doyeong Structural Dynamics, Vol. 11, Issue 3 https://doi.org/10.1063/4.0000249	journal	May 2024
Structure determination of alkali trimers on helium nanodroplets through laser-induced Coulomb explosion Kranabetter, Lorenz; Kristensen, Henrik H.; Schouder, Constant A. The Journal of Chemical Physics, Vol. 160, Issue 13 https://doi.org/10.1063/5.0200389	journal	April 2024
Laser-induced Coulomb explosion imaging of alkali-metal dimers on helium nanodroplets Kristensen, Henrik H.; Kranabetter, Lorenz; Schouder, Constant A. Physical Review A, Vol. 107, Issue 2 https://doi.org/10.1103/PhysRevA.107.023104	journal	February 2023
Time-resolved Coulomb explosion imaging: A method to measure structure and dynamics of molecular nuclear wave packets Stapelfeldt, Henrik; Constant, Eric; Sakai, Hirofumi Physical Review A, Vol. 58, Issue 1 https://doi.org/10.1103/PhysRevA.58.426	journal	July 1998
Laser Coulomb-explosion imaging of small molecules Légaré, F.; Lee, Kevin F.; Litvinyuk, I. V. Physical Review A, Vol. 71, Issue 1 https://doi.org/10.1103/PhysRevA.71.013415	journal	January 2005
Ultrafast Extreme Ultraviolet Induced Isomerization of Acetylene Cations Jiang, Y. H.; Rudenko, A.; Herrwerth, O. Physical Review Letters, Vol. 105, Issue 26 https://doi.org/10.1103/PhysRevLett.105.263002	journal	December 2010
Direct Probe of the Bent and Linear Geometries of the Core-Excited Renner-Teller Pair States by Means of the Triple-Ion-Coincidence Momentum Imaging Technique Muramatsu, Y.; Ueda, K.; Saito, N. Physical Review Letters, Vol. 88, Issue 13 https://doi.org/10.1103/PhysRevLett.88.133002	journal	March 2002
Time-Resolved Double Ionization with Few Cycle Laser Pulses Légaré, F.; Litvinyuk, I. V.; Dooley, P. W. Physical Review Letters, Vol. 91, Issue 9 https://doi.org/10.1103/PhysRevLett.91.093002	journal	August 2003
Visualizing Recurrently Migrating Hydrogen in Acetylene Dication by Intense Ultrashort Laser Pulses Hishikawa, Akiyoshi; Matsuda, Akitaka; Fushitani, Mizuho Physical Review Letters, Vol. 99, Issue 25 https://doi.org/10.1103/PhysRevLett.99.258302	journal	December 2007
Coulomb explosion imaging of small polyatomic molecules with ultrashort x-ray pulses Li, X.; Rudenko, A.; Schöffler, M. S. Physical Review Research, Vol. 4, Issue 1 https://doi.org/10.1103/PhysRevResearch.4.013029	journal	January 2022
Reevaluation of X-Ray Atomic Energy Levels Bearden, J. A.; Burr, A. F. Reviews of Modern Physics, Vol. 39, Issue 1 https://doi.org/10.1103/RevModPhys.39.125	journal	January 1967
Diabolical conical intersections Yarkony, David R. Reviews of Modern Physics, Vol. 68, Issue 4 https://doi.org/10.1103/RevModPhys.68.985	journal	October 1996
Wigner distribution of self-amplified spontaneous emission free-electron laser pulses and extracting its autocorrelation Serkez, Svitozar; Gorobtsov, Oleg; Rivas, Daniel E. Journal of Synchrotron Radiation, Vol. 28, Issue 1 https://doi.org/10.1107/S160057752001382X	journal	January 2021
Harmonic radiation contribution and X-ray transmission at the Small Quantum Systems instrument of European XFEL Baumann, Thomas M.; Boll, Rebecca; De Fanis, Alberto Journal of Synchrotron Radiation, Vol. 30, Issue 4 https://doi.org/10.1107/S1600577523003090	journal	May 2023
Formation and Direct Repair of UV‐induced Dimeric DNA Pyrimidine Lesions Kneuttinger, Andrea Christa; Kashiwazaki, Gengo; Prill, Stefan Photochemistry and Photobiology, Vol. 90, Issue 1 https://doi.org/10.1111/php.12197	journal	December 2013
Photochemical and Photodynamical Properties of Sulfur-Substituted Nucleic Acid Bases, Ashwood, Brennan; Pollum, Marvin; Crespo-Hernández, Carlos E. Photochemistry and Photobiology, Vol. 95, Issue 1 https://doi.org/10.1111/php.12975	journal	September 2018
Direct Determination of Absolute Molecular Stereochemistry in Gas Phase by Coulomb Explosion Imaging Pitzer, M.; Kunitski, M.; Johnson, A. S. Science, Vol. 341, Issue 6150 https://doi.org/10.1126/science.1240362	journal	September 2013
Coulomb Explosion Imaging of Small Molecules Vager, Z.; Naaman, R.; Kanter, E. P. Science, Vol. 244, Issue 4903 https://doi.org/10.1126/science.244.4903.426	journal	April 1989
Role of Postreplicative DNA Mismatch Repair in the Cytotoxic Action of Thioguanine Swann, Peter F.; Waters, Timothy R.; Moulton, David C. Science, Vol. 273, Issue 5278 https://doi.org/10.1126/science.273.5278.1109	journal	August 1996
Observation of the Efimov state of the helium trimer Kunitski, M.; Zeller, S.; Voigtsberger, J. Science, Vol. 348, Issue 6234 https://doi.org/10.1126/science.aaa5601	journal	April 2015
Capturing roaming molecular fragments in real time Endo, Tomoyuki; Neville, Simon P.; Wanie, Vincent Science, Vol. 370, Issue 6520 https://doi.org/10.1126/science.abc2960	journal	November 2020
Laser-Induced Coulomb Explosion Imaging of Aligned Molecules and Molecular Dimers Schouder, Constant A.; Chatterley, Adam S.; Pickering, James D. Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-090419-053627	journal	April 2022
DNA Excited-State Dynamics: From Single Bases to the Double Helix Middleton, Chris T.; de La Harpe, Kimberly; Su, Charlene Annual Review of Physical Chemistry, Vol. 60, Issue 1 https://doi.org/10.1146/annurev.physchem.59.032607.093719	journal	May 2009
Versatile optical laser system for experiments at the European X-ray free-electron laser facility Pergament, M.; Palmer, G.; Kellert, M. Optics Express, Vol. 24, Issue 26 https://doi.org/10.1364/OE.24.029349	journal	January 2016
High-temporal-resolution X-ray spectroscopy with free-electron and optical lasers Rivas, Daniel E.; Serkez, Svitozar; Baumann, Thomas M. Optica, Vol. 9, Issue 4 https://doi.org/10.1364/OPTICA.454920	journal	April 2022
Molecular Dynamics of XFEL-Induced Photo-Dissociation, Revealed by Ion-Ion Coincidence Measurements Kukk, Edwin; Motomura, Koji; Fukuzawa, Hironobu Applied Sciences, Vol. 7, Issue 5 https://doi.org/10.3390/app7050531	journal	May 2017
Photophysics and Photochemistry of Canonical Nucleobases’ Thioanalogs: From Quantum Mechanical Studies to Time Resolved Experiments Arslancan, Serra; Martínez-Fernández, Lara; Corral, Inés Molecules, Vol. 22, Issue 6 https://doi.org/10.3390/molecules22060998	journal	June 2017

Similar Records

Synthetic approaches to a carboranyl thiouracil

Journal Article · Sat Jul 01 04:00:00 UTC 1989 · Pigment Cell Research; (USA) · OSTI ID:5261452

Wilson, J G

Core-Level Spectroscopy of 2-Thiouracil at the Sulfur L1- and L2,3-Edges Utilizing a SASE Free-Electron Laser

Journal Article · Tue Oct 26 00:00:00 UTC 2021 · Molecules · OSTI ID:1828079

Lever, Fabiano; Mayer, Dennis; Metje, Jan; +14 more

Thymic cell activity of thiouracil-treated chicks

Conference · Sat Mar 01 04:00:00 UTC 1986 · Fed. Proc., Fed. Am. Soc. Exp. Biol.; (United States) · OSTI ID:5457970

Scott, T; Glick, B

Related Subjects

Chemical physics
Excited states
Photochemistry

Title: Direct observation of ultrafast symmetry reduction during internal conversion of 2-thiouracil using Coulomb explosion imaging

Citation Formats

References (51)

Similar Records

Related Subjects