Reactions of solvated electrons initiated by sodium atom ionization at the vacuum-liquid interface

Solvated electrons are powerful reagents in the liquid phase that break chemical bonds and thereby create additional reactive species, including hydrogen atoms. We explored the distinct chemistry that ensues when electrons are liberated near the liquid surface rather than within the bulk. Specifically, we detected the products resulting from exposure of liquid glycerol to a beam of sodium atoms. The Na atoms ionized in the surface region, generating electrons that reacted with deuterated glycerol, C(3)D(5)(OD)(3), to produce D atoms, D(2), D(2)O, and glycerol fragments. Surprisingly, 43 ± 4% of the D atoms traversed the interfacial region and desorbed into vacuum before attacking C-D bonds to produce D(2).