Density of medium

However, it is known, that in homolytical processes certaine influence on reaction rate has also so-called "cage effect", which is described by density of medium cohesion energy. That was confirmed by generalization of data concerning to influence of solvents upon decomposition rate of benzoyl peroxide [2] or oxidizing processes [3, 4], That is why the data analysis from work [1] is seemed as expedient by means of five parameter equation ... 

What can the ET theory fiot do for us The present state of art of the theoretical development cannot provide a priori values of V and F. For V only rough approximations from quantum mechanical INDO calculations and intermolecular overlap approximations are available, which can at best provide crude estimations of relative values of electronic coupling. The nuclear parameters AE, E and (or rather the weighted density of medium states), which determine F, cannot be calculated yet and one has to rely on analysis of experimental data. 

P. Blaise, O. Henri-Rousseau. Spectral density of medium strength H-bonds. Direct damping and intrinsic anharmonicity of the slow mode. Beyond adiabatic approximation. Chem Phys 256 85-106, 2000. 

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