Energy and chemical force profiles from the Marcus equation

A detailed analysis of the mechanism of a carbocationic triple shift rearrangement

“…Clearly, the greatest amount of electronic reorganization occurs in the transition state region where the REF shows two minima and two maxima, this is consistent with previous observations of the prevalence of the electronic activity over the structural reordering within the transition state region. [9][10][11][12][13][14][15][16][17] Also it is worth pointing out that REF mostly evolves through negative values indicating that most of the electronic activity is not spontaneous. Overall the REF profile presents four negative peaks and three positive ones, this shows that the determinant chemical events for the progress of the reaction are non-spontaneous bond weakening/breaking processes.…”

The reaction force: Three key points along an intrinsic reaction coordinate

“…It is conceptually useful to apply this relationship to V(R c ). [4][5][6][7][8][9] ()()/. ccc RVRR =−∂∂ F (1) We refer to F(R c ) as the "reaction force;" it is shown in figures 1b and 2b.…”

Decomposition of the electronic activity in competing [5,6] and [6,6] cycloaddition reactions between C60 and cyclopentadiene

“…Computation of F (ξ) is possible by obtaining an energy profile through the intrinsic reaction coordinate procedure (IRC≡ ξ) [37][38][39], which allows one to obtain the minimum energy path for the transformation of reactants into products passing by a transition state. The RF formalism allows the partitioning of the reaction coordinate into different regions where different reaction events might be taking place [40][41][42]. The boundaries of reaction regions are obtained from the critical points on the F (ξ) profile, a minimum at ξ 1 before the transition state and a maximum at ξ 2 thereafter [43].…”