Reassessment of the Four-Point Approach to the Electron-Transfer Marcus–Hush Theory

[Image: see text] The Marcus–Hush theory has been successfully applied to describe and predict the activation barriers and hence the electron-transfer (ET) rates in several physicochemical and biological systems. This theory assumes that in the ET reaction, the geometry of the free Gibbs energy landscape is parabolic, with equal curvature near the local minimum for both reactants and products. In spite of its achievements, more realistic models have included the assumption of the two parabolas having not the same curvature. This situation is analyzed by the Nelsen’s four-point method. As a benchmark to compare the Marcus–Hush approximation to a precise calculation of the excitation energy, we studied the non-ET process of the electronic excitation of the aluminum dimer that has two local minima ((3)∑(g)(–) and (3)∏(u) electronic states) and allows to obtain analytically the Marcus–Hush nonsymmetric parameters. We appraise the ability of the Marcus–Hush formula to approximate the analytical results by using several averages of the two reorganization energies associated with the forward and backward transitions and analyze the error. It is observed that the geometric average minimizes the relative error and that the analytical case is recovered. The main results of this paper are obtained by the application of the Nelsen’s four-point method to compute the reorganization energies of a large set of potential π-conjugated molecules proposed for organic photovoltaic devices using the above-mentioned averages for the Marcus–Hush formula. The activation energies obtained with the geometric average are significantly larger for some donor–acceptor pairs in comparison with the previously employed arithmetic average, their differences being suitable for experimental testing.