Tert-butyl nitrite surface photochemistry: The transition from submonolayer to multilayer behavior

摘要: The photochemistry of tert-butyl nitrite, (CH3)3CONO, adsorbed on Ag(111) at 355 nm has been studied using time-of-flight and reflection adsorption infrared spectroscopy (RAIRS) for coverages ranging from 0.1 to 50 ML. For all a thermal hyperthermal NO desorption distribution is observed due photodissociation. component originates molecules the first second layer, which were trapped by silver substrate. cross section photodissociation independent coverage matches gas phase value. This consistent with direct excitation into S1 state. exceeding 5 ML outermost layers still dissociate, but RAIRS shows that in more inward caging preventing dissociation. Due only isomerization nitrite allowed, as evident RAIRS.