Abstract
Through monitoring the IR emission from vibrationally excited radicals generated by exothermic photolysis reactions, the CN stretch (ν1) and the CO stretch (ν2) vibrational bands of the cyanooxomethyl radical (OCCN) have been observed for the first time at 2093 cm1 and 1774 cm1, respectively. The OCCN radical was produced through 193 nm photolysis of methyl cyanoformate (NCC(O)OCH3), carbonyl cyanide (NCC(O)CN), and pivaloyl cyanide (NCC(O)C(CH3)3). The IR emission spectra were recorded by using nanosecond time-resolved Fourier transform IR emission spectroscopy. Assignments of the spectral peaks were made based on observed time and pressure dependences of IR emission intensities, ab initio calculations, and two-dimensional cross-spectra correlation analysis. Key words: radical, cyanooxomethyl, OCCN, time-resolved vibrational spectroscopy, FTIR, substituted carbonyl dissociation reactions, two-dimensional cross-spectra correlation analysis
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