Solvation Structure and UV–Visible Absorption Spectra of the Nitrate Anion at the Air–Ice Interface by First-Principles Molecular Simulations

Nitrate is a significant contaminant in Polar snow. Its photolysis in environmental sunlight generates reactive nitrogen, which impacts the oxidative capacity of the atmosphere, influencing the fate and lifetimes of pollutants. The photolysis of nitrate can produce either NO2 or NO2–, with recent experiments suggesting that the process is accelerated at the air–ice interface compared to the bulk solution. In this study, we employed a multiscale modeling approach to investigate the enhanced photoreactivity of nitrate at the ice surface in the presence of two different cations. We characterized the solvation shell of NO3– and explored its pairing with cations in water and ice using ab initio molecular dynamics and enhanced sampling. Molecular trajectories were used to calculate light absorption spectra at different solvation conditions and finite temperature. Our analysis revealed that the pairing of nitrate with cations may alter the molar absorption coefficient of nitrate at the air–ice interface affecting the rate of photolysis observed in experiments of ammonium nitrate deposited on snow.