Water jump reorientation and ultrafast vibrational spectroscopy

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• 作者：Damien Laage^a ; ^{damien.laage@ens.fr} ; Guillaume Stirnemann^a ; James T. Hynes^a ; ^b ; ^{hynes@spot.colorado.edu}
• 关键词：Water dynamics ; Hydrogen-bond dynamics ; Pump-probe infrared spectroscopy ; Two-dimensional infrared spectroscopy
• 刊名：Journal of Photochemistry and Photobiology A ; Chemistry
• 出版年：2012
• 期刊代码：66_10106030
• 类别：ch
• 出版时间：15 April, 2012
• 卷：234
• 期：Complete
• 页码：75-82
• 文件大小：831 K

摘要

The reorganization of water's hydrogen-bond (HB) network by breaking and making HBs lies at the heart of many of the pure liquid's special features and many aqueous media phenomena, including chemical reactions, ion transport and protein activity. An essential role in this reorganization is played by water molecule reorientation, long described by very small angular displacement Debye rotational diffusion. A markedly contrasting picture has been recently proposed, based on simulation and analytic modeling: a sudden, large amplitude jump mechanism, in which the reorienting water molecule rapidly exchanges HB partners in an activated process which has all the hallmarks of a chemical reaction. In this contribution, we offer a brief review of the jump mechanism together with a discussion of its application to, and probing by, modern ultrafast infrared spectroscopy experiments. Special emphasis is given to the direct characterization of the jumps via pioneering two-dimensional infrared spectroscopic measurements.