Solvent effects on electronically excited states: QM/Continuum versus QM/Explicit models

The inclusion of solvent effects in the calculation of excited states is vital to obtain reliable absorption spectra and density of states of solvated chromophores. Here we analyze the performance of three classical approaches to describe aqueous solvent in the calculation of the absorption spectra and density of states of pyridine, tropone, and tropothione. Specifically, we compare the results obtained from quantum mechanics/polarizable continuum model (QM/PCM) versus quantum mechanics/molecular mechanics (QM/MM) in its electrostatic-embedding (QM/MMee) and polarizable-embedding (QM/MMpol) fashions, against full-QM computations, in which the solvent is described at the same level of theory as the chromophore. We show that QM/PCM provides very accurate results describing the excitation energies of ππ∗ and nπ∗ transitions, the last ones dominated by strong hydrogen-bonding effects, for the three chromophores. The QM/MMee approach also performs very well for both types of electronic transitions, although the description of the ππ∗ ones is slightly worse than that obtained from QM/PCM. The QM/MMpol approach performs as well as QM/PCM for describing the energy of ππ∗ states, but it is not able to provide a satisfactory description of hydrogen-bonding effects on the nπ∗ states of pyridine and tropone. The relative intensity of the absorption bands is better accounted for by the explicit-solvent models than by the continuum-solvent approach.LG and JJN further acknowledge the University of Vienna for financial support, while MDV and MFSJM thank the Marie Curie Actions, within the Innovative Training Network-European Join Doctorate in Theoretical Chemistry and Computational Modelling TCCM-ITN-EJD-642294, for their respective PhD grant