Journal of Physical Chemistry B, Vol.123, No.27, 5841-5847, 2019
Observation of the Chemical Structure of Water up to the Critical Point by Raman Spectroscopic Analysis of Fluid Inclusions
Raman spectra were obtained simultaneously from the liquid and vapor phases of pure water trapped at the critical density (322 kg.m(-3)) within synthetic inclusions in quartz. As these inclusions are heated up to the critical temperature (373.946 degrees C), the liquid phase decreases in density and the maximum of the Raman OH-stretching band increases in wavenumber. Conversely, as the vapor phase increases in density, the maximum of the Raman OH-stretching band decreases in wavenumber. The Raman bands of the liquid and vapor phases converge to a single band at the critical point of water, where the fluid exists as a single phase. A comparison of the band centroids for the vapor and liquid phases of water indicates respective increases and decreases in the amount of hydrogen bonding in these phases as a function of increasing and decreasing density. These effects were further quantified by peak-fitting the Raman OH-stretching peak with five Gaussian components. All the Gaussian components of the liquid phase decrease in amplitude with increasing temperature with the exception of the double donor-single acceptor (H2O)(4) cluster, which increases in amplitude and becomes the most intense component at temperatures above 300 degrees C. The Raman spectra of the vapor phase are dominated by the free OH component at temperatures below 300 degrees C, but, above this temperature, the double donor-single acceptor (H2O)(4) cluster is again the most intense band. The results indicate that a significant quantity of water clusters is present in both liquid and vapor water at high temperatures and that supercritical water can be considered as a mixture of small water clusters [(H2O)(n), n = 1-4] dominated by the double donor-single acceptor (H2O)(4) cluster.