Time-resolved spectra of polar-polarizable chromophores in solution

Abstract

A recently proposed model for steady-state spectra of polar-polarizable chromophores is extended to describe time-resolved spectra. The model, based on a two-state picture for the solute and on a continuum overdamped description for the (polar) solvent, grasps the essential physics of solvation dynamics, as demonstrated by the comparison with experimental spectra. The solute (hyper)polarizability is responsible for spectroscopic features that cannot be rationalized within the standard picture based on a linear perturbative treatment of the solute-solvent interaction. In particular, the temporal evolution of band-shapes and the appearance of temporary isosbestic points, two common puzzling features of observed spectra, are natural consequences of the molecular hyperpolarizability and of the consequent coupling between solvation and vibrational degrees of freedom.