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Title: Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy

Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition to the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.
Authors:
 [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [4] ;  [5] ;  [6] ; ORCiD logo [7] ; ORCiD logo [3] ; ORCiD logo [3]
  1. Stanford Univ., Menlo Park, CA (United States)
  2. Univ. of Saskatchewan, Saskatoon, SK (Canada); Curtin Univ., Bentley, WA (Australia)
  3. Univ. of Saskatchewan, Saskatoon, SK (Canada)
  4. Stonybrook Apiary, Pittstown, NJ (United States)
  5. Chevron Energy Technology Co., Richmond, CA (United States)
  6. Tokyo Institute of Technology, Tokyo (Japan)
  7. Univ. at Albany, State Univ. of New York, Albany, NY (United States)
Publication Date:
Grant/Contract Number:
AC02-76SF00515; CHE-1265679; 04632-2014; 05810-2016; GM57375
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 33; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1394076

Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., and George, Graham N.. Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy. United States: N. p., Web. doi:10.1021/jacs.7b05116.
Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., & George, Graham N.. Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy. United States. doi:10.1021/jacs.7b05116.
Sneeden, Eileen Y., Hackett, Mark J., Cotelesage, Julien J. H., Prince, Roger C., Barney, Monica, Goto, Kei, Block, Eric, Pickering, Ingrid J., and George, Graham N.. 2017. "Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy". United States. doi:10.1021/jacs.7b05116. https://www.osti.gov/servlets/purl/1394076.
@article{osti_1394076,
title = {Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy},
author = {Sneeden, Eileen Y. and Hackett, Mark J. and Cotelesage, Julien J. H. and Prince, Roger C. and Barney, Monica and Goto, Kei and Block, Eric and Pickering, Ingrid J. and George, Graham N.},
abstractNote = {Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption spectra of both species are characterized by a uniquely low energy transition at about 2465 eV, which occurs at a lower energy than any previously observed feature at the sulfur K-edge and corresponds to a 1s → 3p transition to the singly occupied molecular orbital of the free radical. In conclusion, our results constitute the first observation of substantial levels of thiyl radicals generated by X-ray irradiation and detected by sulfur K-edge X-ray absorption spectroscopy.},
doi = {10.1021/jacs.7b05116},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 139,
place = {United States},
year = {2017},
month = {7}
}