Theoretical approach to the calculation of vibrational Raman spectra in solution within the Polarizable Continuum Model

A methodology for the theoretical evaluation of vibrational Raman scattering intensities for molecules in solution in the polarizable continuum model (PCM) framework is presented. Raman intensities are expressed in terms of derivatives of the dynamic effective polarizability with respect to nuclear coordinates. Local field effects are included by considering both the solvent polarization induced by the probing field (cavity field) and the solvent reaction field. The dependence of computed Raman intensities on the parameters of the calculation (basis set, exchange-correlation functional for DFT calculations, and cavity size) is discussed. A comparison between PCM and semiclassical values for simple molecules in various solvents is made.