This paper reports results of molecular dynamics simulations on the electrochemical reduction of the tertbutyl bromide molecule according to the scheme: (CH3)(3)CBr + e -> (CH3)(3)C-center dot + Br-. A model Hamiltonian is proposed, that is based on the Anderson-Newns concept of the electron transfer process and on quantum calculations performed for the (CH3)(3)CBr molecule and the (CH3)(3)CBr center dot- radical anion. The rate constants k and the transfer coefficients alpha obtained at different solvent frictions gamma(x) temperatures T and overpotentials eta, are presented. At eta = 1.3 V, which corresponds to the experimental conditions, the alpha estimates obtained from the simulations with low solvent frictions are very close to the measured value of 0.2; in more viscous solvents they are slightly higher. The alpha coefficient is found to depend non-linearly on eta. It is also shown to depend on the temperature: at lower overpotentials the transfer coefficient decreases with T:alpha (348 K) < alpha (298 K) < alpha (248 K), while for high eta the reversed order appears. In all simulations strong saddle point avoidance was observed. The choice of the effective reaction paths is shown to be responsible for some trends found in the results. (C) 2009 Elsevier Ltd. All rights reserved.