On the cluster composition of supercritical water combining molecular modeling and vibrational spectroscopic data

摘要

The present study is aimed at a detailed analysis of supercritical water structure based on the combination of experimental vibrational spectra as well as molecular modeling calculations of isolated water clusters. We propose an equilibrium cluster composition model where supercritical water is considered as an ideal mixture of small water clusters (n=1-3) at the chemical equilibrium and the vibrational spectra are expected to result from the superposition of the spectra of the individual clusters, Thus, it was possible to extract from the decomposition of the midinfrared spectra the evolution of the partition of clusters in supercritical water as a function of density. The cluster composition predicted by this model was found to be quantitatively consistent with the near infrared and Raman spectra of supercritical water analyzed using the same procedure. We emphasize that such methodology could be applied to determine the portion of cluster in water in a wider thermodynamic range as well as in more complex aqueous supercritical solutions.