Energetic Relaxation

The first explanation offered for the phenomenon of dispersive kinetics is that it is caused by a distribution of rates of primary electron transfer, and that the islowi P lifetimes originate from a minority of reaction centres from the islowi tail of this distribution. The energetic basis for this distribution could be an inhomogeneous distribution of a rate-determining parameter such as X, AG or Vda (or any combination of these) (Figure lOA). The principal alternative explanation is that the multiple lifetimes represent a time-dependent energetic relaxation of the P Ha intermediate due... 

Fig. 17 As the triplet exciton energetically relaxes with increasing time after excitation the Ph spectrum shifts accordingly to lower energies. Here, the peak energies of the phosphorescence spectra of a PF2/6 thin film optically excited at 20 K are plotted according to Eq. 2. The slope yields the true width of the triplet DOS, for polyfluorene 40meV. Details are given in [24]...

This is the relaxation time of the polymer oxidation under electro-chemically stimulated conformational relaxation control. So features concerning both electrochemistry and polymer science are integrated in a single equation defining a temporal magnitude for electrochemical oxidation as a function of the energetic terms acting on this oxidation. A theoretical development similar to the one performed for the Butler-Volmer equation yields... 

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