THE COMPUTER-SIMULATION OF CORRELATED ELECTRON-TRANSFER ACROSS THE ELECTRODE ELECTROLYTE INTERFACE INVOLVING MULTIPLE REDOX SPECIES/

The basis for molecular dynamics simulations of the electron transfer between multiple redox species and a metal electrode is developed usin g the Anderson-Newns approach to model the effect of the electronic de grees of freedom. As an example, the free energy surface for 2 redox s pecies coupled to the metal surface and with each other is computed vi a two dimensional umbrella sampling. The resulting free energy surface is found to be qualitatively in agreement with an analytic model for such a process [Y. Boroda, A. Calhoun, and G. A. Voth, J. Chem. Phys. 107, 8940 (1997)], with relatively minor quantitative disagreement. (C ) 1998 American Institute of Physics.