Electronic transitions, local control theory

The kinetics of the reactions of photo-generated CH2CI, CHBrCl, CCI3, and CHsC Cla radicals with CI2 have been measured. In addition, the transition states for the four reactions were localized and optimized at the MP2/6-31G(d,p) level of theory. The kinetics were found to be controlled by the electronic nature of the substituents. ... 

Second, we note that the dynamical aspect of the dielectric response is still incomplete in the above treatment, since (1) no information was provided about the dielectric response frequency and (2) a harmonic oscillator model for the local dielectric response is oversimplified and a damped oscillator may provide a more complete description. These dynamical aspects are not important in equilibrium considerations such as our transition-state-theory level treatment, but become so in other limits such as solvent-control electron-transfer reactions discussed in Section 16.6. 

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