Multiple time-scale behavior of the hydrogen-bond network in water

Abstract

The temperature-dependent changes in the hydrogen-bond network of SPC/E water have been examined using power spectral analysis of fluctuations in tagged-molecule potential energies and local tetrahedral order parameters. The clear signatures of multiple time-scale or 1/ƒ α behavior in the power spectra are shown to depend sensitively on the strength of hydrogen bonding. The analysis focuses on three specific power spectral features:the frequency of crossover to white noise behavior, the exponent in the 1/ƒ α regime, and the librational peak. The exponent of the tagged-particle potential-energy fluctuations is shown to be strongly correlated with the diffusivity in the temperature range of 230 to 300 K. This correlation is strongest in the temperature-density regimes where the mechanism for diffusion is likely to be dominated by translational-rotational coupling, suggesting that the value of the exponent is a measure of the efficiency of the coupling of librational modes with network vibrations. The temperature dependence of all power spectral features was found to be strongest along the 0.9-g cm^-3 isochore, which corresponds closely to the density of minimum diffusivity for the temperature range studied here. The static distributions of the tagged-particle quantities were examined to determine the degree of heterogeneity of the local molecular environment and its relationship with power spectral features.