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Title: Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster

Abstract

The way in which a three-dimensional network of water molecules accommodates an excess proton is hard to discern from the broad vibrational spectra of dilute acids. The sharper bands displayed by cold gas-phase clusters, H+(H2O)n, are therefore useful because they encode the network-dependent speciation of the proton defect and yet are small enough to be accurately treated with electronic structure theory. We identified the previously elusive spectral signature of the proton defect in the three-dimensional cage structure adopted by the particularly stable H+(H2O)21 cluster. Cryogenically cooling the ion and tagging it with loosely bound deuterium (D2) enabled detection of its vibrational spectrum over the 600 to 4000 cm-1 range. The excess charge is consistent with a tricoordinated H3O+ moiety embedded on the surface of a clathrate-like cage.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
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  1. Yale Univ., New Haven, CT (United States). Sterling Chemistry Lab.
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1741040
Grant/Contract Number:  
FG02-06ER15800; FA9550-13-1-0007; CNS 08-21132
Resource Type:
Accepted Manuscript
Journal Name:
Science
Additional Journal Information:
Journal Volume: 344; Journal Issue: 6187; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Clusters; Ions; Water; Infrared Spectroscopy; Mass Spectrometry

Citation Formats

Fournier, Joseph A., Johnson, Christopher J., Wolke, Conrad T., Weddle, Gary H., Wolk, Arron B., and Johnson, Mark A. Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster. United States: N. p., 2014. Web. doi:10.1126/science.1253788.
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Fournier, Joseph A., Johnson, Christopher J., Wolke, Conrad T., Weddle, Gary H., Wolk, Arron B., & Johnson, Mark A. Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster. United States. https://doi.org/10.1126/science.1253788
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Fournier, Joseph A., Johnson, Christopher J., Wolke, Conrad T., Weddle, Gary H., Wolk, Arron B., and Johnson, Mark A. Fri . "Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster". United States. https://doi.org/10.1126/science.1253788. https://www.osti.gov/servlets/purl/1741040.
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@article{osti_1741040,
title = {Vibrational spectral signature of the proton defect in the three-dimensional H+(H2O)21 cluster},
author = {Fournier, Joseph A. and Johnson, Christopher J. and Wolke, Conrad T. and Weddle, Gary H. and Wolk, Arron B. and Johnson, Mark A.},
abstractNote = {The way in which a three-dimensional network of water molecules accommodates an excess proton is hard to discern from the broad vibrational spectra of dilute acids. The sharper bands displayed by cold gas-phase clusters, H+(H2O)n, are therefore useful because they encode the network-dependent speciation of the proton defect and yet are small enough to be accurately treated with electronic structure theory. We identified the previously elusive spectral signature of the proton defect in the three-dimensional cage structure adopted by the particularly stable H+(H2O)21 cluster. Cryogenically cooling the ion and tagging it with loosely bound deuterium (D2) enabled detection of its vibrational spectrum over the 600 to 4000 cm-1 range. The excess charge is consistent with a tricoordinated H3O+ moiety embedded on the surface of a clathrate-like cage.},
doi = {10.1126/science.1253788},
journal = {Science},
number = 6187,
volume = 344,
place = {United States},
year = {Fri May 30 00:00:00 EDT 2014},
month = {Fri May 30 00:00:00 EDT 2014}
}
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https://doi.org/10.1126/science.1253788
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