Energy relaxation versus spectral diffusion of the OH-stretching vibration of HOD in liquid-to-supercritical deuterated water
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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- October 2005
- DOI:
- Bibcode:
- 2005JChPh.123p1105S
- Keywords:
-
- 61.25.Em;
- 78.30.Cp;
- 65.20.+w;
- 77.22.Ch;
- 77.84.Nh;
- Molecular liquids;
- Liquids;
- Thermal properties of liquids: heat capacity thermal expansion etc.;
- Permittivity;
- Liquids emulsions and suspensions;
- liquid crystals