Mechanism and kinetics of electrochemical reduction of tert-butyl bromide molecule - improvement of theoretical model

摘要: Abstract In the present article earlier formulated theoretical model of adiabatic electrochemical reduction tert-butyl bromide molecule [1] is improved. The potential energy profiles describing dissociation C-Br bond in neutral and anion, which previous work were based on quantum calculations performed vacuo, are replaced with new ones, derived from similar calculations, but taking into account solvent (dimethyl sulfoxide) effects. modified two-dimensional surfaces introduced simulation program rate constants re-examined for three different values reorganization energies λ : 0.624, 1.0 1.41324 eV. results found to differ significantly those reported previously, exhibiting now better agreement experimental estimates activation transfer coefficient α . New calculated interval overpotentials η  = 1.3-1.45 V decrease 0.262 0.237 when  = 0.624 eV, 0.305 0.273  = 1 eV, 0.332 0.308  = 1.41324 eV (the latter obtained approximately). shown also temperature, this effect much weaker than our study [2] Some trends explained by saddle point avoidance phenomenon.