4.6 Article

Dissimilar Dynamics of Coupled Water Vibrations

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JOURNAL OF PHYSICAL CHEMISTRY A
卷 113, 期 22, 页码 6260-6265

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AMER CHEMICAL SOC
DOI: 10.1021/jp900480r

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Dissimilar dynamics of coupled stretch vibrations of a water molecule are revealed by two-dimensional, IR correlation spectroscopy. These are caused by essentially non-Gaussian fluctuations of the electric field exerted by the environment on the individual OH stretch vibrations. Non-Gaussian statistics of the individual site frequency fluctuations results in distinctively different dephasing of the symmetric and asymmetric eigenmodes. This phenomenon can only be described if the assumption of Gaussian dynamics in the traditional theories is abandoned.

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