An efficient and robust procedure to calculate absorption spectra of aqueous charged species applied to NO2−

Abstract

Accurate calculation of absorption spectra of aqueous NO₂⁻ requires rigorously sampling the quantum potential energy surfaces for microsolvation of NO₂⁻ with at least five explicit water molecules and embedding the resulting clusters in a continuum solvent accounting for the statistical weighted contributions of individual isomers. This method, which we address as ASCEC + PCM, introduces several desired features when compared against MD simulations derived QM/MM spectra: comparatively fewer explicit solvent molecules to be treated with expensive QM methods, the identification of equilibrium structures in the quantum PES to be used in further vibrational spectroscopy, and the unequivocal identification of cluster orbitals undergoing electronic transitions and charge transfer that originate the spectral bands.