A. A. Raskovalov, A. A. Latypov.
ABSTRACT:
In the paper application of non-constant force field molecular dynamics is shown for studying of redox reactions in liquid (molten) media. The method was applied to a system of ions. Interaction between these ions consisted of short-range Lennard-Jones and Coulombic pair potentials. Electron transfer between donor-acceptor pairs is implemented via special algorithms. Simulation results showed that concentrations of interacting ions changed during the simulations and reached some stationary values. Comparison between thermodynamics and the simulated results has revealed that difference in own energies of ions must include not only EMF value but additional terms too. It was shown that stationary concentrations depended on temperature, starting ion concentrations and a value of a solvent ionic radius. It was shown that the method can separate electronic transfer between different kinds of donor-acceptor pairs. In some simulations a system demonstrated behavior similar to Marcus “inverted region”.
KEYWORDS:
non-constant force field molecular dynamics, redox reactions, electron transfer, melt, Marcus theory
DOI: 10.1134/S0235010618060063