The v_1 and v_2 vibrational bands of the OCCN radical detected through time-resolved Fourier transform IR emission spectroscopy

摘要

Through monitoring the IR emission from vibrationally excited radicals generated by exothermic photolysis reactions,the CN stretch (V_1) and the CO stretch (v_2) vibrational bands of the cyanooxomethyl radical (OCCN) have been observed for the first time at 2093 cm~(-1) and 1774 cm~(-1),respectively.The OCCN radical was produced through 193 nm photolysis of methyl cyanoformate (NCC(O)OCH_3),carbonyl cyanide (NCC(O)CN),and pivaloyl cyanide (NCC(O)C(CH_3)_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.