DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H 2 O) n , n ≤ 200, by Electronic Absorption Spectroscopy

Abstract

Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. Innsbruck (Austria)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1591822
Grant/Contract Number:  
AC02-05CH11231; CHE-1663832
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 45; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; optical absorption; absorption; molecular structure; cluster chemistry; absorption spectroscopy

Citation Formats

Herburger, Andreas, Barwa, Erik, Ončák, Milan, Heller, Jakob, van der Linde, Christian, Neumark, Daniel M., and Beyer, Martin K. Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H 2 O) n –, n ≤ 200, by Electronic Absorption Spectroscopy. United States: N. p., 2019. Web. doi:10.1021/jacs.9b10347.
Herburger, Andreas, Barwa, Erik, Ončák, Milan, Heller, Jakob, van der Linde, Christian, Neumark, Daniel M., & Beyer, Martin K. Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H 2 O) n –, n ≤ 200, by Electronic Absorption Spectroscopy. United States. https://doi.org/10.1021/jacs.9b10347
Herburger, Andreas, Barwa, Erik, Ončák, Milan, Heller, Jakob, van der Linde, Christian, Neumark, Daniel M., and Beyer, Martin K. Fri . "Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H 2 O) n –, n ≤ 200, by Electronic Absorption Spectroscopy". United States. https://doi.org/10.1021/jacs.9b10347. https://www.osti.gov/servlets/purl/1591822.
@article{osti_1591822,
title = {Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H 2 O) n –, n ≤ 200, by Electronic Absorption Spectroscopy},
author = {Herburger, Andreas and Barwa, Erik and Ončák, Milan and Heller, Jakob and van der Linde, Christian and Neumark, Daniel M. and Beyer, Martin K.},
abstractNote = {Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.},
doi = {10.1021/jacs.9b10347},
journal = {Journal of the American Chemical Society},
number = 45,
volume = 141,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share: