A reaction or process generating free radicals (or some other reactive reaction intermediates) which then induce a chain reaction. For example, in the chlorination of alkanes by a radical mechanism the initiation step is the dissociation of molecular chlorine.
PAC, 1994, 66, 1077. 'Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)' on page 1125 (https://doi.org/10.1351/pac199466051077)
PAC, 1996, 68, 149. 'A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996)' on page 169 (https://doi.org/10.1351/pac199668010149)