Spectroscopic probing and diagnostics of the geometric structure of the alkoxy and alkyl peroxy radical intermediates

摘要: The recent spectroscopy of the small to moderate sized alkoxy and peroxy organic radicals is reviewed. Rotationally resolved laser induced fluorescence spectra intermediates have been obtained in cold supersonic expansions. This rotational structure allows unambiguous assignment observed spectral transitions particular isomers conformers a given chemical species. Unfortunately no excited electronic states that fluoresce. However there an transition near IR gives rise sharp absorption spectra, which can be detected using cavity ringdown spectroscopy. Since these experiments performed at room temperature, congestion prevents resolution structure. Nonetheless careful comparison between quantum chemistry calculations origins vibrational frequencies allow probable many bands conformers. For both alkox...