Large-scale computer simulation of an electrochemical bond-breaking reaction

A novel Hamiltonian is employed to explicitly simulate an electrochemical bond-breaking reaction in which an electron-transfer reaction is directly coupled to the dissociation of a molecular species. The free energy surface as a function of both the collective solvation coordinate of the electron transfer and the intramolecular bond length of a CH3Cl molecule is computed by virtue of a classical molecular dynamics (MD) simulation. The method is also easily generalized to treat a variety of electrochemically catalyzed phenomenon. The simulation data show very significant deviations from the predictions of standard analytical theory.