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Journal of Electroanalytical Chemistry, Vol.599, No.2, 376-376, 2007
Ion transfer across liquid-liquid interfaces from transition-state theory and stochastic molecular dynamics simulations (vol 590, pg 138, 2006)
We investigate the kinetics and dynamics of ion transfer across liquid-liquid interfaces. We calculate the potential of mean force (pmf) of ion transfer from Monte Carlo simulations of a lattice-gas model, assuming independent chemical and electrostatic contributions. The shape of the pmf justifies considering the transfer as activated. The kinetics are obtained from transition-state theory and independently from stochastic molecular dynamics simulations. Both methods yield consistent results, with straight Tafel plots and friction effects in line with Kramers' theory, but stronger than for a diffusing particle. A higher friction makes barrier recrossing more likely.