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Ion-Specific Long-Range Correlations on Interfacial Water Driven by Hydrogen Bond Fluctuations

Enami, Shinichi and Colussi, Agustín J. (2014) Ion-Specific Long-Range Correlations on Interfacial Water Driven by Hydrogen Bond Fluctuations. Journal of Physical Chemistry B, 118 (7). pp. 1861-1866. ISSN 1520-6106.

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Some of the most important processes in nature involve interfacial water. It has long been conjectured that specific ion effects therein are associated with the unique properties of interfacial water. Here we reveal the mechanism of such association by showing that the strength of ion-specific long-range correlations tracks the amplification of fluctuations on the surface of water-alcohol mixtures at the percolation thresholds of their hydrogen-bonded water networks. We used in situ online electrospray mass spectrometry to determine χ = [I–]/[Br–] ratios in microfilms of (NaI + NaBr) solutions in water–methanol (ME) and water–isopropanol (IP) mixtures as functions of x_(ME) and x_(IP) molar fractions, and the addition of NaClO_4. We found that, beginning at 0.1 μM, ClO_4^– has detectable effects on χ that peak at x_(ME) ~ 0.40, x_(IP)~ 0.15, i.e., at water percolation thresholds where fluctuations maximize mean water cluster sizes and, hence, interionic connections. The stronger correlations between ions of similar surface propensities suggest that correlations propagate preferentially along 2-D interfacial layers.

Item Type:Article
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URLURL TypeDescription
Enami, Shinichi0000-0002-2790-7361
Colussi, Agustín J.0000-0002-3400-4101
Additional Information:© 2014 American Chemical Society. Received: November 19, 2013. Revised: January 17, 2014. Published: January 29, 2014. Publication Date (Web): January 29, 2014. This work was financially supported by the Japan Science Technology Agency (JST) PRESTO program, Kurita Water and Environment Foundation, and the U.S.A. National Science Foundation grant AGS-1238977. We are grateful to Dr. Himanshu Mishra, Prof. Michael Hoffmann, and Prof. William Goddard of Caltech and Dr. Tetsuya Hama of Hokkaido University for stimulating discussions.
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Japan Science Technology Agency (JST) PRESTO programUNSPECIFIED
Kurita Water and Environment FoundationUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20140407-102611079
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Official Citation:Ion-Specific Long-Range Correlations on Interfacial Water Driven by Hydrogen Bond Fluctuations Shinichi Enami and Agustín J. Colussi The Journal of Physical Chemistry B 2014 118 (7), 1861-1866
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44687
Deposited By: Ruth Sustaita
Deposited On:07 Apr 2014 17:56
Last Modified:03 Oct 2019 06:21

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