Reactions of hydrocarbon radicals and biradicals

Experimental measurements of the rate coefficients for several types of gas phase radical reactions are reviewed. They include radical isomerization and dissociation, radical + radical association, and unimolecular reactions of peroxy radicals. Some reactions of methylene in its lowest singlet state are also considered. The links to theories of chemical reaction rates and especially of capture rates for radical + radical reactions are examined. Many of the reactions involve formation of adducts, which can isomerize and dissociate. Such reactions frequently involve energy distributions of the adducts that are far from Boltzmann, and the interpretation of measurements requires the use of master equation techniques. The basis of these methods and the use of matrix diagonalization and eigenvector/eigenvalue analysis to extract phenomenological rate coefficients are discussed. The relevance of the measurements to applications in atmospheric chemistry and, especially, in combustion is briefly considered.