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

A novel Hamiltonian is employed to explicitly simulate an electrochemical b ond-breaking reaction in which an electron-transfer reaction is directly co upled to the dissociation of a molecular species. The free energy surface a s a function of both the collective solvation coordinate of the electron tr ansfer and the intramolecular bond length of a CH3Cl molecule is computed b y virtue of a classical molecular dynamics (MD) simulation. The method is a lso easily generalized to treat a variety of electrochemically catalyzed ph enomenon. The simulation data show very significant deviations from the pre dictions of standard analytical theory. (C) 1999 Elsevier Science B.V. All rights reserved.