Vibrational relaxation studies in methyl acetate: Role of microenvironment and hydrodynamic forces

The Raman spectra were recorded for the CO stretching vibration of methyl acetate as solutions in various polar and non-polar solvents. The isotropic component was obtained and the vibrational relaxation rates were calculated. On the basis of dependence of isotropic Raman bandwidth on the hydrodynamic properties of the solute-solvent systems, the information was obtained on the microenvironment prevailing in the neighborhood of the CO stretching mode. Significant correlation is observed between vibrational relaxation rate and solvent parameters namely viscosity, density, refractive index and molecular radius. Microviscosity, involving the size of solute and solvent molecules, is found to be crucial in determining the bandwidth, hence the relaxation rate. The microenvironment appears to play an important role in the vibrational relaxation process.