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  • Title: Energy relaxation versus spectral diffusion of the OH-stretching vibration of HOD in liquid-to-supercritical deuterated water.
    Author: Schwarzer D, Lindner J, Vöhringer P.
    Journal: J Chem Phys; 2005 Oct 22; 123(16):161105. PubMed ID: 16268674.
    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 temperature and solvent density by femtosecond mid-infrared spectroscopy. Using the dielectric constant of the fluid both, the OH-stretching absorption frequency and the VER rate, 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/formation is much faster than VER.
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