Electron-induced dissociation of tert-butyl nitrite adsorbed on Ag(1 1 1)

The electron-induced chemistry of tert-butyl nitrite (TBN, (CH3)3CONO), adsorbed on Ag(1 1 1), or over a CH3OH spacer layer, was studied at 90 K using three kinds of measurements––the time dependence of ejected fragments during 70 eV electron irradiation, temperature-programmed desorption (TPD) after irradiation, and X-ray photoelectron spectroscopy before and after irradiation. Only NO is detected during 70 eV electron irradiation, and the initial total cross-section for loss of TBN is quite large, 3.3×10−15 cm2. Post-irradiation TPD, after dissociating ∼90% of a saturated TBN monolayer, reveals residual TBN and a number of products, including NO, C4H8 (isobutene), CH3COCH3 (acetone), (CH3)3COH (t-butyl alcohol), CO and H2O. Interestingly, there is no evidence for H2 in TPD. Illustrating a central role for the Ag(1 1 1) substrate, electron-induced dissociation of monolayer TBN adsorbed over 10 ML of methanol was less efficient, by a factor of 4, than 1 ML TBN on clean Ag(1 1 1).