In this study, we use Monte Carlo track chemistry simulations to show that "dry" secondary electrons, precursors of the "hydrated" electron (e<sup>-</sup><sub>aq</sub>), can be scavenged on the sub-picosecond time scale prior to hydration, by a high concentration (>0.1-1 M) of azide ions (N<sub>3</sub><sup>-</sup>) in water irradiated with <sup>60</sup>Co γ-rays and <sup>3</sup>H β-electrons at 25 °C. This is a striking result, as N<sub>3</sub><sup>-</sup> is known to react very slowly with e<sup>-</sup><sub>aq</sub>. These processes tend to significantly reduce the yields of H<sub>2</sub> as observed experimentally. For both energetic Compton electrons ("linear energy transfer", LET ∼ 0.3 keV/μm), which are generated by the cobalt-60 γ-rays, and <sup>3</sup>H β-electrons (LET ∼ 6 keV/μm), our H<sub>2</sub> yield results confirm previous Monte Carlo simulations, which indicated the necessity of including the capture of the precursors to e<sup>-</sup><sub>aq</sub>. Interestingly, our calculations show no significant changes in the scavenging of "dry" electrons at high azide concentrations in passing from γ-radiolysis to tritium β-radiolysis (<i>i.e.</i>, with LET). This led us to the conclusion that the higher H<sub>2</sub> yield observed experimentally for <sup>3</sup>H β-electrons compared to <sup>60</sup>Co γ-rays is explained mainly by the difference in the radiation track structures during the chemical stage (>1 ps). The higher LET of tritium β-electrons leads to more molecular products (H<sub>2</sub> in this case) in tritium radiolysis than in γ-radiolysis. Finally, a value of 0.5 nm was derived for the reaction distance between N<sub>3</sub><sup>-</sup> and the “dry” electron from the H<sub>2</sub> yields observed in <sup>60</sup>Co γ-radiolysis at high N<sub>3</sub><sup>-</sup> concentrations.