Experimental reorganization

Comparison between Experimental Reorganization Parameters for some Electrochemical and Homogeneous Exchange Reactions... 

Altman J (1975a) Experimental reorganization of the cerebellar cortex. V. Effects of early X-irradiation schedules that allow or prevent the acquisition of basket cells. J. Comp. Neurol., 165, 31-48. 

Additional insight into the various energetic contributions to X may be derived from the temperature dependence of k. Within the Marcus framework, it is possible to extract the enthalpy of reorganization of the protein from the observed activation enthalpy. The reorganization enthalpies for cytochrome c and azurin have an upper limit of about 0.3 eV (7 kcal/mol), whereas the value for myoglobin is about 0.9 eV (20 kcal/mol) (77). The experimental reorganization energy for cytochrome c is consistent with a theoretical prediction of this value obtained... 

Because the rates of chemical reactions are controlled by the free energy of the transition state, information about the stmcture of transition states is crucial to understanding reaction mechanism. However, because transition states have only transitory existence, it is not possible to make experimental measurements that provide direct information about their structure.. Hammond has discussed the circumstances under which it is valid to relate transition-state stmcture to the stmcture of reactants, intermediates, and products. His statements concerning transition-state stmcture are known as Hammond s postulate. Discussing individual steps in a reaction mechanism, Hammond s postulate states if two states, as, for example, a transition state and an unstable intermediate, occur consecutively during a reaction process and have neariy the same energy content, their interconversion will involve only a small reorganization of molecular stmcture. ... 

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