Dynamic properties of hydrogen-bonded networks in supercritical water
Dynamic properties of supercritical water at temperatures between 573 and 773 K and densities between 0.49 and 0.83 g/cm(3) have been investigated by molecular dynamics simulation and compared to states located on the vapor-liquid coexistence curve. A flexible simple point charge potential has been assumed for interactions in the subcritical states, whereas a reparameterization of that model has been performed to model the supercritical states. The hydrogen bonding structure and the diffusion coefficients in an ensemble of simulated states were previously analyzed and a good agreement with available experimental data was found. Dynamic properties of hydrogen bonding like the bond lifetimes and the influence of hydrogen bonds in the vibrational spectra are discussed along a range of simulation conditions. A nonlinear behavior of the hydrogen-bond lifetime as a function of temperature is observed in subcritical water whereas a linear dependence is found in supercritical water. Special attention is paid to the intermolecular vibrational spectrum (10-400 cm(-1)). It has been observed that the mode centered at 200 cm(-1), attributed to the intermolecular O-O stretching vibration in the ambient state remains active in the supercritical states.
Marti
J
Departament de Fisica i Enginyeria Nuclear, Universitat Politecnica de Catalunya, B5-206 Campus Nord, 08034 Barcelona, Catalonia, Spain* and Department of Chemistry, University of California, Berkeley, California 94720-1460, U.