Vibronic coupling and spin sublevel decay rates

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Abstract
The rate expression for nonradiative decay is reformulated to provide a representation in which the initial state wavefunction most faithfully reflects the states that are actually prepared in experiment. The expression is given in an exact golden‐rule form in terms of dressed final states. The Schrödinger equation for the dressed states determines those couplings among final basis functions which have a significant effect on the rates. We consider applications to the T1 →S0 radiative and nonradiative decays in nitrogen‐heterocyclic compounds to show how the individual spin sublevel decay rates can be altered as a result of changes in T1−T2(3nπ* −3ππ*) vibronic coupling.