Photofragmentation of Nitryl Chloride in the Ultraviolet Regime and Vacuum Ultraviolet Regime

Abstract

Photofragmentation of nitryl chloride (ClNO2) is reported in the ultraviolet (UV) (λ = 240 nm and λ = 308 nm) and in the vacuum ultraviolet (VUV) regime (55 nm ≤ λ ≤ 110 nm, corresponding to the photon energy range 11.3 eV ≤ E ≤ 22.5 eV), where pulsed radiation is used to excite the neutral molecule in the gas phase. The neutral photolysis products that are formed upon UV photolysis are subsequently probed by photoionization mass spectrometry by using time-correlated tunable laser-produced plasma VUV radiation. UV-pump/VUV-probe experiments allow us to identify two primary photolysis channels at λ = 308 nm: (i) Cl + NO2 and (ii) O + ClNO. Primary quantum yields for atomic product formation are deduced from photoionization experiments for both channels: γ308 nm(Cl) = 0.93 ± 0.10, and γ308 nm(O) = 0.07 ± 0.01. The yield of Cl formation (N(Cl)) is significantly reduced relative to that of O formation (N(O)) at λ = 240 nm, corresponding to a N(Cl)/N(O) ratio of 1.44 ± 0.15. The atomic oxygen is found to be formed in its 3P ground state at both photolysis wavelengths. The present results are compared to earlier work, and atmospheric implications of the present results are briefly discussed. The tunable VUV light source also allows us to perform photoionization mass spectrometry experiments on nitryl chloride without primary photolysis. These experiments yield the first ionization energy of ClNO2 as well as fragmentation thresholds of ClNO2+.