Anisotropy shift and Raman bandwidth studies in carbonyl containing molecule o-chlorobenzaldehyde: role of repulsive forces.

The analysis of Raman anisotropy shift as a function of solvent concentration shows the weakening of pair interaction of the molecules due to the influence of solvent-induced perturbations. The present study deals with the effect of dielectric constant of the medium on the non-coincidence effect (anisotropy shift) and the role of van der Waals' volume on the anisotropic Raman bandwidth. The CO stretching vibration of o-chlorobenzaldehyde (OCBD) molecule was studied in various polar and non-polar solvents namely CCl4, CH3CN, C6H5Cl and CH3C6H5. The data on anisotropic bandwidth are interpreted using the van der Waals' volume within the framework of lineshape theory of Bratos and Tarjus, while the Onsager-Fröhlich model on non-coincidence effect has been tested. Our study shows that the repulsive potential of the type e-alphaR is playing an important role in the OCBD-solvent interactions. The vanishing of anisotropy shift (non-coincidence effect) on dilution may be explained on the basis of repulsive forces playing a significant role in solute-solvent interactions.