Hydrogen Bond Breaking Dynamics of the Water Trimer in the Translational and Librational Band Region of Liquid Water

The effect of exciting each of the three classes of intermolecular vibrations on the hydrogen bond lifetime (τH) of the isolated water trimer is investigated by far-infrared laser spectroscopy. Single excitation of a librational vibration decreases τH by 3 orders of magnitude to τH = 1−6 ps, compara...

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Bibliographic Details
Published in:	Journal of the American Chemical Society Vol. 123; no. 25; pp. 5938 - 5941
Main Authors:	Keutsch, Frank N, Fellers, Ray S, Brown, Mac G, Viant, Mark R, Petersen, Poul B, Saykally, Richard J
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 27-06-2001
Subjects:	Hydrogen Bonding Lasers Models, Molecular Molecular Conformation Spectrophotometry, Infrared Vibration Water - chemistry
Online Access:	Get full text
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Summary:	The effect of exciting each of the three classes of intermolecular vibrations on the hydrogen bond lifetime (τH) of the isolated water trimer is investigated by far-infrared laser spectroscopy. Single excitation of a librational vibration decreases τH by 3 orders of magnitude to τH = 1−6 ps, comparable to the time scale of a number of important bulk water dynamical relaxation processes. In contrast, excitation of translational or torsional vibrations has no significant effect (τH = 1−2 ns). Although such a dependence of τH on intermolecular motions has also been proposed for liquid water via computer simulations, these are the first experiments that provide a detailed molecular picture of the respective motions without extensive interpretation.
Bibliography:	istex:2B24C4A587B0977E0B81B13ACBE49C5C3C844F5A ark:/67375/TPS-PLVZ8ZFG-F ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0002-7863 1520-5126
DOI:	10.1021/ja003683r