Reactivity of quasi-free electrons toward N₃^- and its impact on H₂ formation mechanism in water radiolysis

Picosecond pulse radiolysis measurements were employed to assess the effectiveness of N-3- in scavenging quasi-free electrons in aqueous solutions. The absorption spectra of hydrated electrons were recorded within a 100 ps timeframe across four distinct solutions with N-3- concentrations of 0.5, 1, 2, and 5 M in water. The results revealed a concentration-dependent shift in the maximum absorption spectra of fully solvated electrons. Notably, at 5 M concentration, the maximum absorption occurred at 670 nm, in contrast to 715 nm observed for water. Intriguingly, the formation yield of hydrated electrons within the initial 5 ps electron pulse remained unaffected, showing that, even at a concentration of 5 M, N-3- does not effectively scavenge quasi-free electrons. This is in disagreement with conclusions from stochastic models found in the literature. This observation has an important impact on understanding the mechanism of H-2 formation in water radiolysis, which we discuss briefly here.