Interaction induced Raman light scattering as a probe of the local density structure of binary supercritical solutions

Interaction induced Raman light scattering is presented as a unique tool for the understanding of solvation processes from the solute's point of view in weakly interacting solute-solvent systems. A review of pertinent literature shows that this technique should be useful at least in single-phase binary mixtures such as supercritical solutions. Methane is used here as a probe molecule at 10mol% concentration (as the solute) and 90mol% CO and CO₂ are the solvents. The light scattering results, i.e., the dependence of the anisotropic intensities divided by density (I/d) on the density, are interpreted by use of the Duh-Haymet-Henderson closure (bridge) function of the Ornstein-Zernike integral equation. These data, together, are examined in the context of known supercritical solution thermodynamics and statistical mechanical results. It is shown that the light scattering I/d data versus density yield maxima in both attractive and repulsive solute-solvent systems. The local number density maxima were found near these same densities by the integral equation calculations for both methane + carbon monoxide or carbon dioxide using only Lennard-Jones single-centre parameters as input. The methane + carbon monoxide system is identified as weakly attractive (augmenting), whereas the methane + carbon dioxide system is identified as repulsive (avoidance).