Accurate Steady-State and Zero-Time Fluorescence Spectra of Large Molecules in Solution by a First-Principle Computational Method

We report the first-principle calculation and analysis of the vibrationally-resolved steady-state absorption and fluorescence spectra, and of the zero-time fluorescence spectrum of a sizeable molecule, Coumarin C153, in two different solvents. Our approach, bringing together the most recent developments in the fields of Time Dependent Density Functional Theory and of polarizable continuum solvent models, with an efficient method for the computation of vibrational contributions to transition intensities, allows a remarkable agreement with experiments, both concerning the lineshapes and the solvatochromic and Stokes shifts. The method is also able to nicely describe the solvent relaxation effect on the fluorescence spectra, perfectly reproducing the energy shift between zero-time and steady-state fluorescence