The kinetic amplification offered by the S(RN)1 chain process allows the investigation of initiation electron-transfer/bond-breaking steps under very unfavorable thermodynamic conditions, which escape standard kinetic methods. Combining these observations with those derived under conventional thermodynamic conditions allows a considerable extension of the driving force window and thus opens the possibility of uncovering new mechanistic and reactivity patterns. The "thermal" S(RN)1 reaction of 4-nitrobenzyl chloride with 2-nitropropanate ions is an illustrating example where two problems of current interest could be investigated. One of these concerns the actively investigated and debated question of the dichotomy and connections between S(N)2 reactions and single electron transfer, particularly the question of catalysis of dissociative electron transfer that may result from mechanism bifurcation along an S(N)2 pathway. The other deals with the existence and magnitude of attractive interactions between fragments within the solvent and the influence of these interactions on the dynamics of dissociative electron transfer. Testing systematically the various mechanistic possibilities through simulation of product distribution and half-reaction time led to the conclusion that a small but sizable interaction between fragments within the solvent cage does exist and influences the dynamics of the dissociative electron-transfer reaction quite significantly. While similar effects have been uncovered or suspected in the electrochemical reductions of CCl4, of other benzyl halides and of phenacyl halides, the reduction of 4-nitrobenzyl chloride by the 2-nitropropanate ion provides a first example of the influence of an interaction between caged fragments on the dynamics of an homogeneous dissociative electron-transfer reaction. The simulations required a precise determination of the various rate constants involved in the chain process. Most of them were derived from cyclic voltammetry and redox catalysis. Particular care was exerted to estimate the ranges of uncertainty on these determinations and hence evaluate the reliability of the mechanistic conclusions.