SIMULATION OF THE ELECTRON-TRANSFER PROCESS CU2-ARROW-CU++CU2+ IN AQUEOUS-SOLUTION(+CU+REVERSIBLE)

A Monte Carlo simulation is performed to investigate the role of solve nt in the Cu2+/Cu+ electron exchange process in water. This study is b ased on the classical Marcus model using the energy gap between the re actant and product states as the reaction coordinate. Since the proces s has a rather high activation free energy, conventional simulations a re not best suited to its complete description, and thus special sampl ing techniques are required. In this case, a mapping potential is used to drive the system from the reactants to the transition state, and f ree energies are computed by thermodynamic perturbation and thermodyna mic integration methods. A comparison is made between the results obta ined by both methods and conclusions are drawn concerning the applicab ility of the Marcus model to this kind of process.