Flash photolysis and triplet states and free radicals in solution

A personal account is given of the development of microsecond flash photolysis in George Porter’s laboratory at Cambridge in the early 1950s. This made possible, for the first time, the observation of the absorption spectra of the lowest triplet states of many polycyclic aromatic hydrocarbons in fluid solutions. The T–T transitions were found to be very intense with oscillator strengths approaching unity in many cases. Detailed kinetic studies showed that triplet state decay was first order and viscosity dependent and strongly quenched by dissolved oxygen. Several aromatic free radicals such as benzyl were also observed in liquid solution for the first time. The advent of the laser in the early 1960s made it possible to extend flash photolysis studies to the ns and ps and eventually the fs time range. Such studies have revolutionized the study of excited states and free radicals and have made possible advances in the understanding of the dynamics of chemical and biological systems that would have been unimaginable 60 years ago.