Vibrational and Electronic Spectra of Neutral and Ionic Combustion Reaction Intermediates Trapped in Rare-Gas Matrixes

The infrared absorptions of neutral and ionic molecules trapped in solid rare-gas matrixes lie close to the gas-phase band centers, and perturbations in valence electronic transitions are relatively small. Since molecular diffusion through rare-gas solids is inhibited, matrix isolation studies provide a valuable tool for obtaining the infrared and visible-ultraviolet spectra of combustion reaction intermediates. The results of studies of the spectra of HCO, trans-HOCO, HCC, C2-, CO2+, CO2-, C2H2+, C3H4+, HCOOH+, HOCO+, and HCO2- summarized in this Account illustrate the importance of supplementing familiar generalizations with experimental observations.