Two-dimensional fluorescence spectroscopy for the identification of discharge intermediates

Abstract

A protocol is developed for the identification of discharge intermediates from complex electronic spectra. The protocol involves resonant ionisation mass spectrometry to determine the mass of the unknown carrier followed by a two-dimensional fluorescence spectrum which is used as a "map" to guide higher resolution techniques. High resolution dispersed fluorescence provides accurate ground electronic state vibrational frequencies which are then compared with theoretical calculations of frequencies and structures of a range of isomers consistent with the observed mass. The protocol is demonstrated in the first identification of the cis and trans-1-vinylpropargyl radicals as a ubiquitous radical in hydrocarbon discharges.