Abstract
The dynamics of vibrational energy relaxation (VER) of the OH-stretching vibration of HOD in liquid-to-supercritical heavy water is studied as a function of solvent density and temperature by femtosecond mid-infrared spectroscopy. Using the dielectric constant of the fluid both, the VER rate and the OH-stretching absorption frequency, can be correlated phenomenologically with the average hydrogen-bond connectivity within the random D2O-network. This correlation enables the identification of thermodynamic conditions under which spectral diffusion due to hydrogen-bond breakage or formation is much faster than VER.
© 2006 Optical Society of America
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