Photochemistry of N2O4 Adsorbed on Ice Surfaces at 193 nm

Abstract

A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO2 was adsorbed as N2O4 approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO2, NO, O2 and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO2, NO and O2 were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO2 was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N2O4. NO was supposed to be a predissociation product from the electronically excited NO2 prepared through the photodissociation of N2O4.