On stability of water and heavy-water nanoclusters in a nitrogen cryomatrix

Earlier studies of the properties of cryocondensed films of diluted solutions of ethanol in nitrogen have shown that a slight increase in the temperature of solid nitrogen, long before its sublimation, leads to changes in the vibrational spectrum of ethanol. The present work is a continuation of these studies and is focused on exploring the properties of thin films of cryovacuum condensates of dilute solutions of water and heavy water in nitrogen. The measurements were carried out in the temperature range from 12 to 40 K; the pressure in the vacuum chamber was below 5 x 10(-8) Torr. The concentration of water and heavy water in nitrogen was varied in the range from 0.5% to 3%. Based on the analysis of the vibrational spectra, it is suggested that the structure of the two-component film is a system of polyaggregates. An increase in the temperature of the matrix leads to the transformation of these polyaggregates into more stable states, as indicated by the changes in the fine structure of the bands. The presence of the absorption bands with the frequencies corresponding to the water monomers and dimers in a nitrogen matrix can be due to the fact that a fraction of the water molecules constituting polyaggregates might not be connected through hydrogen bonds with the neighboring molecules, forming broken chains. Thus, a population of quasi-free molecules with the corresponding absorption bands is formed. It is assumed that these unbound quasi-free molecules are mainly located in the subsurface layer of the clusters. (C) 2014 AIP Publishing LLC.