Stereoelectronic, Vibrational, and Environmental Contributions to Polarizabilities of Large Molecular Systems: A Feasible Anharmonic Protocol

Reliable computations of linear and nonlinear optical properties of molecular systems in condensed phases require a proper account of stereoelectronic, vibrational, and environmental effects. In the framework of density functional theory, these effects can be accurately introduced using second-order vibrational perturbation theory in conjunction with polarizable continuum models. We illustrate the combination of an anharmonic description of the ground-state potential energy surface with solvation effects treated with the polarizable continuum model (PCM) in the calculation of the electronic, zero-point, and pure vibrational polarizabilities of selected systems. The description of the solvation environment is enriched by taking into account the dynamical aspects of the solute–solvent interactions through the inclusion of both electronic and vibrational nonequilbrium effects, as well as the direct effect of the solvent on the electric field that generates the molecular response (local field effect). This treatment yields accurate results which can be directly compared with experimental findings without the need of empirical corrections