The UV-Visible Absorption Spectra of Coumarin and Nile Red in Aqueous Solution: A Polarizable QM/MM Study.

Abstract

We present a comprehensive computational study of the UV-visible absorption spectra of 7-methoxycoumarin and Nile red in aqueous solution. Our fully atomistic workflow couples classical molecular dynamics (MD) with polarizable QM/MM based on fluctuating charges (QM/FQ) and dipoles (QM/FQFμ). Ensemble-averaged spectra are constructed from the snapshots extracted from the MD, embedding solvent fluctuations and specific solute-solvent interactions in the electronic response of organic dyes. The spectral profiles, obtained at the various levels, reflect the underlying solute-solvent interactions and dynamics, and we rationalize them in terms of hydrogen bonding and frontier molecular orbitals involved in the main electronic transitions. Finally, the simulated spectra and solvatochromic shifts are compared with the available experimental data, showing an overall good agreement and demonstrating the robustness of the computational protocol.