Source of Molecular Hydrogen in High-Temperature Water Radiolysis

Molecular hydrogen is a primary product of the interaction of low-LET (γ, β) radiation with water, and previous measurements have shown that its initial yield increases at elevated temperature. This has been the subject of controversy because more atomic H and (e(-))aq free radicals escape recombination at elevated temperature, and the corresponding production of H2 should decrease. Room temperature experiments have demonstrated that a large fraction of H2 also comes from early physicochemical processes (presumably electron-hole charge recombination and/or dissociative electron attachment), which can be suppressed by scavenging presolvated electrons. In the present work we extend these scavenging measurements up to 350 °C to investigate why the H2 yield increases. We find that most of the H2 yield increase is due to the "presolvation" processes. Relatively small changes in the scavenging efficiency vs LET, and a significant effect of temperature depending on the (positive or negative) charge of the scavenger, indicate that the presolvation H2 is dominated by electron-hole charge recombination rather than dissociative electron attachment at all temperatures.