Enabling forbidden processes: quantum and solvation enhancement of nitrate anion UV absorption

We present simulated electronic absorption spectra of isolated and solvated nitrate anion in the UV region, focusing primarily on the absorption into the first absorption band around 300 nm. This weak absorption band in this spectral region is responsible for the generation of NOx in the polar areas or OH(•) radicals in the hydrosphere. The 300 nm absorption band is symmetrically strongly forbidden and coupling of at least two vibrational modes is needed to allow the transition in the isolated nitrate anion. Further symmetry breaking is provided by solvation. In this study we model the absorption spectra of nitrate-water clusters using the combined reflection principle path integral molecular dynamics (RP-PIMD) method. Condensed phase UV spectra are modeled within a cluster-continuum model. The calculated spectra are compared with experimental bulk phase measurements and reasonable agreement is found. We also provide a benchmarking of the DFT functionals to be used for a description of the electronically excited states of solvated nitrate anion.