Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; Cordones, Amy A.; Cho, Hana; Lee, Jae Hyuk; Schoenlein, Robert W.; Khalil, Munira

doi:10.1063/1.4983157

Title: Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

Journal Article · Mon May 08 00:00:00 EDT 2017 · Structural Dynamics

DOI:https://doi.org/10.1063/1.4983157· OSTI ID:1379901

Van Kuiken, Benjamin E. ^[1]; Ross, Matthew R. ^[1]; Strader, Matthew L. ^[2]; Cordones, Amy A. ^[2]; Cho, Hana ^[2]; Lee, Jae Hyuk ^[2]; Schoenlein, Robert W. ^[2]; Khalil, Munira ^[1]

Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Ultrafast X-ray Science Lab., Chemical Sciences Division

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (~2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps) and decays within 6 ns. The second transient species forms on a timescale of ~400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowestlying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0002190; AC02-76SF00515

OSTI ID:: 1379901

Alternate ID(s):: OSTI ID: 1361883; OSTI ID: 1369310

Journal Information:: Structural Dynamics, Vol. 4, Issue 4; ISSN 2329-7778

Publisher:: American Crystallographic Association/AIPCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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References (58)

Intermolecular photochemical proton transfer in solution: new insights and perspectives Hynes, James T.; Tran-Thi, Thu-Hoa; Granucci, Giovanni Journal of Photochemistry and Photobiology A: Chemistry, Vol. 154, Issue 1 https://doi.org/10.1016/S1010-6030(02)00304-0	journal	December 2002
Sulfur K-Edge X-ray Absorption Spectroscopy of 2Fe−2S Ferredoxin: Covalency of the Oxidized and Reduced 2Fe Forms and Comparison to Model Complexes Anxolabéhère-Mallart, Elodie; Glaser, Thorsten; Frank, Patrick Journal of the American Chemical Society, Vol. 123, Issue 23 https://doi.org/10.1021/ja010472t	journal	June 2001
Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser: Application to Spin Crossover Dynamics Lemke, Henrik T.; Bressler, Christian; Chen, Lin X. The Journal of Physical Chemistry A, Vol. 117, Issue 4 https://doi.org/10.1021/jp312559h	journal	January 2013
Probing the hydrogen-bond network of water via time-resolved soft X-ray spectroscopy Huse, Nils; Wen, Haidan; Nordlund, Dennis Physical Chemistry Chemical Physics, Vol. 11, Issue 20 https://doi.org/10.1039/b822210j	journal	January 2009
Probing the Electronic Structure of a Photoexcited Solar Cell Dye with Transient X-ray Absorption Spectroscopy Van Kuiken, Benjamin E.; Huse, Nils; Cho, Hana The Journal of Physical Chemistry Letters, Vol. 3, Issue 12 https://doi.org/10.1021/jz300671e	journal	June 2012
The Advanced Light Source (ALS) Slicing Undulator Beamline Heimann, P. A.; Glover, T. E.; Plate, D. SYNCHROTRON RADIATION INSTRUMENTATION: Ninth International Conference on Synchrotron Radiation Instrumentation, AIP Conference Proceedings https://doi.org/10.1063/1.2436277	conference	January 2007
Spectroscopic and DFT Studies of Second-Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Nonlocal Electrostatic Contributions to Reduction Potentials Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M. Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja306438n	journal	October 2012
Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex Bressler, Ch.; Milne, C.; Pham, V. -T. Science, Vol. 323, Issue 5913 https://doi.org/10.1126/science.1165733	journal	January 2009
Picosecond X-ray Absorption Spectroscopy of a Photoinduced Iron(II) Spin Crossover Reaction in Solution Khalil, Munira; Marcus, Matthew A.; Smeigh, Amanda L. The Journal of Physical Chemistry A, Vol. 110, Issue 1 https://doi.org/10.1021/jp055002q	journal	January 2006
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Tracking excited-state charge and spin dynamics in iron coordination complexes Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe Nature, Vol. 509, Issue 7500 https://doi.org/10.1038/nature13252	journal	May 2014
The crystal structure of α-thiopyridone Penfold, B. R. Acta Crystallographica, Vol. 6, Issue 8 https://doi.org/10.1107/S0365110X5300199X	journal	September 1953
Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses Canton, Sophie E.; Kjær, Kasper S.; Vankó, György Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7359	journal	March 2015
Recent Experimental Advances on Excited-State Intramolecular Proton Coupled Electron Transfer Reaction Hsieh, Cheng-Chih; Jiang, Chang-Ming; Chou, Pi-Tai Accounts of Chemical Research, Vol. 43, Issue 10 https://doi.org/10.1021/ar1000499	journal	October 2010
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkin Trans. 2, Issue 5 https://doi.org/10.1039/P29930000799	journal	January 1993
2-Pyridinethiol/2-Pyridinethione Tautomeric Equilibrium. A Comparative Experimental and Computational Study Moran, Damian; Sukcharoenphon, Kengkaj; Puchta, Ralph The Journal of Organic Chemistry, Vol. 67, Issue 25 https://doi.org/10.1021/jo0263768	journal	December 2002
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin Shadle, Susan E.; Penner-Hahn, James E.; Schugar, Harvey J. Journal of the American Chemical Society, Vol. 115, Issue 2 https://doi.org/10.1021/ja00055a057	journal	January 1993
Spin-state studies with XES and RIXS: From static to ultrafast Vankó, György; Bordage, Amélie; Glatzel, Pieter Journal of Electron Spectroscopy and Related Phenomena, Vol. 188 https://doi.org/10.1016/j.elspec.2012.09.012	journal	June 2013
Diagonalisation of the Dirac Hamiltonian as a basis for a relativistic many-body procedure Heully, J. -L; Lindgren, I.; Lindroth, E. Journal of Physics B: Atomic and Molecular Physics, Vol. 19, Issue 18 https://doi.org/10.1088/0022-3700/19/18/011	journal	September 1986
Recent advances on ultrafast X-ray spectroscopy in the chemical sciences Chen, L. X.; Zhang, X.; Shelby, M. L. Chem. Sci., Vol. 5, Issue 11 https://doi.org/10.1039/C4SC01333F	journal	January 2014
Excited-State Proton Transfer: From Constrained Systems to “Super” Photoacids to Superfast Proton Transfer ^† Tolbert, Laren M.; Solntsev, Kyril M. Accounts of Chemical Research, Vol. 35, Issue 1 https://doi.org/10.1021/ar990109f	journal	January 2002
Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey Journal of the American Chemical Society, Vol. 132, Issue 19 https://doi.org/10.1021/ja101381a	journal	May 2010
Ultrafast Independent N−H and N−C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering Eckert, Sebastian; Norell, Jesper; Miedema, Piter S. Angewandte Chemie International Edition, Vol. 56, Issue 22 https://doi.org/10.1002/anie.201700239	journal	April 2017
Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes: Deciphering the Interplay of Electronic and Structural Dynamics Huse, Nils; Cho, Hana; Hong, Kiryong The Journal of Physical Chemistry Letters, Vol. 2, Issue 8 https://doi.org/10.1021/jz200168m	journal	March 2011
Time-Resolved X-ray Spectroscopy in the Water Window: Elucidating Transient Valence Charge Distributions in an Aqueous Fe(II) Complex Van Kuiken, Benjamin E.; Cho, Hana; Hong, Kiryong The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02509	journal	January 2016
Biporous polymeric microspheres coupled with mercaptopyridine for rapid chromatographic purification of plasmid DNA Li, Yuan; Dong, Xiao-Yan; Sun, Yan Journal of Applied Polymer Science, Vol. 104, Issue 4 https://doi.org/10.1002/app.24417	journal	January 2007
Picosecond X-ray absorption measurements of the ligand substitution dynamics of Fe(CO)5 in ethanol Ahr, Brian; Chollet, Matthieu; Adams, Bernhard Physical Chemistry Chemical Physics, Vol. 13, Issue 13 https://doi.org/10.1039/c0cp01856b	journal	January 2011
Poly[diaquatris(μ ₄ -isophthalato)dilanthanum(III)] Fan, Le-Qing; Wu, Ji-Huai Acta Crystallographica Section E Structure Reports Online, Vol. 66, Issue 2 https://doi.org/10.1107/S1600536809054543	journal	January 2010
Observing Photochemical Transients by Ultrafast X-Ray Absorption Spectroscopy Saes, Melanie; Bressler, Christian; Abela, Rafael Physical Review Letters, Vol. 90, Issue 4 https://doi.org/10.1103/PhysRevLett.90.047403	journal	January 2003
Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A. Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.6b12992	journal	March 2017
Rotational and Core Level Spectroscopies As Complementary Techniques in Tautomeric/Conformational Studies: The Case of 2-Mercaptopyridine Melandri, Sonia; Evangelisti, Luca; Maris, Assimo Journal of the American Chemical Society, Vol. 132, Issue 30 https://doi.org/10.1021/ja104484b	journal	August 2010
Energies and alkylations of tautomeric heterocyclic compounds: old problems - new answers Beak, Peter Accounts of Chemical Research, Vol. 10, Issue 5 https://doi.org/10.1021/ar50113a006	journal	May 1977
Sulfur K-Edge XAS and DFT Calculations on [Fe ₄ S ₄ ] ²⁺ Clusters: Effects of H-bonding and Structural Distortion on Covalency and Spin Topology Dey, Abhishek; Roche, Cara L.; Walters, Marc A. Inorganic Chemistry, Vol. 44, Issue 23 https://doi.org/10.1021/ic050981m	journal	November 2005
ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud Annual Review of Physical Chemistry, Vol. 56, Issue 1 https://doi.org/10.1146/annurev.physchem.56.092503.141314	journal	May 2005
Equilibration studies. Protomeric equilibria of 2- and 4-hydroxypyridines, 2- and 4-hydroxypyrimidines, 2- and 4-mercaptopyridines, and structurally related compounds in the gas phase Beak, Peter; Fry, Fred S.; Lee, Jaekeun Journal of the American Chemical Society, Vol. 98, Issue 1 https://doi.org/10.1021/ja00417a027	journal	January 1976
Structural Determination of a Photochemically Active Diplatinum Molecule by Time-Resolved EXAFS Spectroscopy van der Veen, Renske M.; Milne, Chris J.; El Nahhas, Amal Angewandte Chemie International Edition, Vol. 48, Issue 15 https://doi.org/10.1002/anie.200805946	journal	March 2009
Interaction of 2- and 4-Mercaptopyridine with Pentacyanoferrates and Gold Nanoparticles ^† Nunes, Fábio Souza; Bonifácio, Leonardo Da Silva; Araki, Koiti Inorganic Chemistry, Vol. 45, Issue 1 https://doi.org/10.1021/ic0512429	journal	January 2006
2-Thiopyridone: X-ray and neutron diffraction study Ohms, U.; Guth, H.; Kutoglu, A. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 3 https://doi.org/10.1107/S0567740882004166	journal	March 1982
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O. Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.020	journal	January 2005
Ultrafast conversions between hydrogen bonded structures in liquid water observed by femtosecond x-ray spectroscopy Wen, Haidan; Huse, Nils; Schoenlein, Robert W. The Journal of Chemical Physics, Vol. 131, Issue 23 https://doi.org/10.1063/1.3273204	journal	December 2009
Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO) ₅ and Its Parent Compound Mn ₂ (CO) ₁₀ Cho, Hana; Hong, Kiryong; Strader, Matthew L. Inorganic Chemistry, Vol. 55, Issue 12 https://doi.org/10.1021/acs.inorgchem.6b00208	journal	June 2016
Sulfur and Chlorine K-Edge X-ray Absorption Spectroscopic Studies of Photographic Materials Smith, Teresa A.; DeWitt, Jane G.; Hedman, Britt Journal of the American Chemical Society, Vol. 116, Issue 9 https://doi.org/10.1021/ja00088a020	journal	May 1994
Regular Two-Component Pauli-Like Effective Hamiltonians in Dirac Theory Chang, Ch; Pelissier, M.; Durand, Ph Physica Scripta, Vol. 34, Issue 5 https://doi.org/10.1088/0031-8949/34/5/007	journal	November 1986
Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution Wernet, Ph.; Kunnus, K.; Josefsson, I. Nature, Vol. 520, Issue 7545 https://doi.org/10.1038/nature14296	journal	April 2015
Resonance Raman Spectroscopic and Theoretical Investigation of the Excited State Proton Transfer Reaction Dynamics of 2-Thiopyridone Du, Rui; Liu, Chong; Zhao, Yanying The Journal of Physical Chemistry B, Vol. 115, Issue 25 https://doi.org/10.1021/jp203185a	journal	June 2011
Recent experimental and theoretical developments in time-resolved X-ray spectroscopies Milne, C. J.; Penfold, T. J.; Chergui, M. Coordination Chemistry Reviews, Vol. 277-278 https://doi.org/10.1016/j.ccr.2014.02.013	journal	October 2014
Photochemical Processes Revealed by X-ray Transient Absorption Spectroscopy Chen, Lin X.; Zhang, Xiaoyi The Journal of Physical Chemistry Letters, Vol. 4, Issue 22 https://doi.org/10.1021/jz401750g	journal	November 2013
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
PHOTOCHEMISTRY OF 2-MERCAFTOPYRIDINES. PART 2. AN EPR AND SPIN-TRAPPING INVESTIGATION USING 2-METHYL-2-NITROSOPROPANE AND aci-NITROMETHANE AS SPIN TRAPS IN AQUEOUS SOLUTIONS REszka, Krzysztof J.; Chignell, Colin F. Photochemistry and Photobiology, Vol. 60, Issue 5 https://doi.org/10.1111/j.1751-1097.1994.tb05132.x	journal	November 1994
Analogs of Aspergillic Acid. IV. Substituted 2-Bromopyridine-N-oxides and Their Conversion to Cyclic Thiohydroxamic Acids ¹ Shaw, Elliott; Bernstein, Jack; Losee, Kathryn Journal of the American Chemical Society, Vol. 72, Issue 10 https://doi.org/10.1021/ja01166a008	journal	October 1950
Ultrafast Chemistry: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud ChemInform, Vol. 37, Issue 3 https://doi.org/10.1002/chin.200603268	journal	January 2006
Selective Toxicity O'Brien, Richard D. Toxic Phosphorus Esters: Chemistry, Metabolism, and Biological Effects https://doi.org/10.1016/b978-1-4832-2774-0.50013-0	book	January 1960
Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays Smolentsev, Grigory; Milne, Christopher J.; Guda, Alexander Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15998-z	journal	May 2020
Orbital-specific mapping of the ligand exchange dynamics of $Fe(CO)_{5}$ in solution Wernet, Ph.; Kunnus, K.; Josefsson, I. Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2016-04896	text	January 2015
Structural Determination of a Photochemically Active Diplatinum Molecule by Time-Resolved EXAFS Spectroscopy van der Veen, Renske M.; Milne, Chris J.; El Nahhas, Amal Angewandte Chemie, Vol. 121, Issue 15 https://doi.org/10.1002/ange.200805946	journal	March 2009
Selective Toxicity Mant, Timothy G. K.; Lewis, Lionel D.; Ritter, James M. Clinical Pharmacology and Therapeutics: Questions for Self Assessment, Third edition https://doi.org/10.1201/b13551-11	book	April 2008
Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering Eckert, Sebastian; Norell, Jesper; Miedema, Piter S. Universität Potsdam https://doi.org/10.25932/publishup-43687	text	January 2021

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