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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b10347· OSTI ID:1591822
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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1591822
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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