Solid state and solution nitrate photochemistry: photochemical evolution of the solid state lattice.

We examined the deep UV 229 nm photochemistry of NaNO(3) in solution and in the solid state. In aqueous solution excitation within the deep UV NO(3)¯ strong π → π* transition causes the photochemical reaction NO(3)¯ → NO(2)¯ + O·. We used UV resonance Raman spectroscopy to examine the photon dose dependence of the NO(2)¯ band intensities and measure a photochemical quantum yield of 0.04 at pH 6.5. We also examined the response of solid NaNO(3) samples to 229 nm excitation and also observe formation of NO(2)¯. The quantum yield is much smaller at ∼10(-8). The solid state NaNO(3) photochemistry phenomena appear complex by showing a significant dependence on the UV excitation flux and dose. At low flux/dose conditions NO(2)¯ resonance Raman bands appear, accompanied by perturbed NO(3)¯ bands, indicating stress in the NaNO(3) lattice. Higher flux/dose conditions show less lattice perturbation but SEM shows surface eruptions that alleviate the stress induced by the photochemistry. Higher flux/dose measurements cause cratering and destruction of the NaNO(3) surface as the surface layers are converted to NO(2)¯. Modest laser excitation UV beams excavate surface layers in the solid NaNO(3) samples. At the lowest incident fluxes a pressure buildup competes with effusion to reach a steady state giving rise to perturbed NO(3)¯ bands. Increased fluxes result in pressures that cause the sample to erupt, relieving the pressure.