Quantum Confinement Effects on Solvatochromic Shifts of Molecular Solutes

Abstract

We demonstrate the pivotal role of quantum mechanics density confinement effects on solvatochromic shifts. In particular, by resorting to a quantum mechanics/molecular mechanics (QM/MM) approach capable of accounting for confinement effects we successfully reproduce vacuo-to-water solvatochromic shifts for dark n → π* and bright π → π* transitions of acrolein and dark n → π* transitions of pyridine and pyrimidine without the need of including explicit water molecules in the QM portion. Remarkably, our approach is also able to dissect the effects of the single forces acting on the solute–solvent couple and allows for a rationalization of the experimental findings in terms of physicochemical quantities.