Computing the inhomogeneous broadening of electronic transitions in solution: a first-principle quantum mechanical approach

摘要

Starting from Marcus's relationship connecting the inhomogeneous broadening with the solvent reorganization energy and exploiting recent state-specific developments in PCM/TD-DFT calculations, we propose a procedure to estimate the polar broadening of optical transitions. When applied to two representative molecular probes, coumarin C153 and 4-aminophthal-imide, in different solvents, our approach provides for the polar broadening values fully consistent with the experimental ones. Thanks to these achievements, for the first time fully ab initio vibrationally resolved absorption spectra in solution are computed, obtaining spectra for coumarin C153 in remarkable agreement with experiments.