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

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 cons...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2010-07, Vol.133 (3), p.034103-034103-9
Main Authors: Tassaing, T., Garrain, P. A., Bégué, D., Baraille, I.
Format: Article
Language:English
Subjects:
Chemical Sciences
Models, Molecular
Molecular Conformation
or physical chemistry
Quantum Theory
Spectrophotometry, Infrared
Spectrum Analysis
Spectrum Analysis, Raman
Theoretical and
Vibration
Water - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.3457483