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IR Spectroscopic Properties of H(MeOH)n+ Clusters in the Liquid Phase: Evidence for a Proton Wire

✍ Scribed by Evgenii S. Stoyanov; Irina V. Stoyanova; Christopher A. Reed


Publisher
John Wiley and Sons
Year
2008
Tongue
English
Weight
588 KB
Volume
14
Category
Article
ISSN
0947-6539

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✦ Synopsis


Abstract

The long‐standing problem of understanding the nature of the “excess proton” in acidified water is simplified by studying the proton in methanol. The 3D network of hydrogen bonds in H~(aq)~^+^ is reduced to a 1D problem. Infrared spectroscopic characterization of linear chain methanol proton solvates in H(CH~3~OH)~n~^+^ for n=2–8 provides insight into some of the puzzling IR spectral features associated with O‐H‐O vibrations. These include the virtual disappearance of otherwise strong bands from H‐bonded methanol molecules adjacent to symmetrical O‐H^+^‐O groups. The data indicate that a chain of up to four OH⋅⋅⋅O bonds either side of this group can act as an electrical wire to separate positive charge. This suggests a refinement of the Grotthuss proton‐hopping mechanism for explaining the anomalously high mobility of H^+^ in H‐bonded media.