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

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.
Authors:
 [1] ;  [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [2] ;  [1]
  1. Department of Chemistry, University of Washington, Seattle, Washington 98195, USA
  2. Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Publication Date:
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231; SC0002190
Type:
Accepted Manuscript
Journal Name:
Structural Dynamics
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2329-7778
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1379901
Alternate Identifier(s):
OSTI ID: 1361883; OSTI ID: 1369310

Van Kuiken, Benjamin E., Ross, Matthew R., Strader, Matthew L., Cordones, Amy A., Cho, Hana, Lee, Jae Hyuk, Schoenlein, Robert W., and Khalil, Munira. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer. United States: N. p., Web. doi:10.1063/1.4983157.
Van Kuiken, Benjamin E., Ross, Matthew R., Strader, Matthew L., Cordones, Amy A., Cho, Hana, Lee, Jae Hyuk, Schoenlein, Robert W., & Khalil, Munira. Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer. United States. doi:10.1063/1.4983157.
Van Kuiken, Benjamin E., Ross, Matthew R., Strader, Matthew L., Cordones, Amy A., Cho, Hana, Lee, Jae Hyuk, Schoenlein, Robert W., and Khalil, Munira. 2017. "Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer". United States. doi:10.1063/1.4983157. https://www.osti.gov/servlets/purl/1379901.
@article{osti_1379901,
title = {Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer},
author = {Van Kuiken, Benjamin E. and Ross, Matthew R. and Strader, Matthew L. and Cordones, Amy A. and Cho, Hana and Lee, Jae Hyuk and Schoenlein, Robert W. and Khalil, Munira},
abstractNote = {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.},
doi = {10.1063/1.4983157},
journal = {Structural Dynamics},
number = 4,
volume = 4,
place = {United States},
year = {2017},
month = {5}
}

Works referenced in this record:

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994
  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001