Calculation of triplet–triplet energy transfer rates from emission and absorption spectra. The quenching of hemicarcerated triplet biacetyl by aromatic hydrocarbons

Abstract

The kinetics of triplet–triplet (T–T) energy transfer have been analysed with a view to linking theories of chemical reactions (involving the rupture and formation of bonds) with theories of processes, such as electron transfer or energy transfer, which preserve chemical bonding. As for the latter, our analysis does not support the claim that, of the two rival expressions for T–T energy transfer, both rooted in the golden rule, only one is applicable to electron transfer or T–T transfer. Though the two expressions do reflect different standpoints, the distinction is eroded by the assumption of a delta-function distribution for the vibrational spectrum. It is shown that theories of chemical reactions also furnish estimates of Franck–Condon factors; rates of chemical reactions and chemical processes are both related to the properties (strengths and lengths) of the reactive bonds, but differ in the mode of energy dissipation. The relationship between the rates of reactions and processes presents new possibilities for a unified view of chemical reactivity.