In silico characterization of bimolecular electron transfer reactions: The ferrocene-ferrocenium reaction as a test case

摘要

The theoretical modeling of chemical reactions in condensed phase still represents an open field of investigation for theoretical-computational chemistry. In this context, we have proposed a methodology (the Perturbed Matrix Method [PMM]), based on the first principles of statistical mechanics and on the use of molecular simulations, which has demonstrated its ability in quantitatively predicting the kinetics and the thermodynamics of chemical reactions in complex atomistic environments. In this study, we demonstrate the features of PMM by modeling the resonant Electron Transfer bimolecular reaction between ferrocene and ferrocenium in solution. The obtained results, despite the adopted approximations and the intrinsic limitations of the approach, are in very good agreement with the experimental data and demonstrate the ability of the method for addressing complex reactions in solution and for evaluating the kinetics of slow events out of the potentialities of the state-of-the-art molecular simulations.