Theoretical Study on the Kinetics Parameters of V²⁺ （aq）/V³⁺ （aq）Electron Transfer Reaction

On the basis of the common feature of electron transfer and metal ion hydration processes,an accurate hydration potential function scheme for the determination of various electron transfer kinetics parameters is presented.Two hydration potential functions are determined in terms of the experimental spectroscopic data and the hydration thermodynamics data and are then used to depict the energy dependence of the reacting system on the separation between the central ion and the inner sphere molecules,together with the solvent reorganization.The activation energy is obtained in terms of the proposed new activation model and the hydration potential functions,and is calibrated using the corresponding experimental value extracted from the experimental rate constants,and is also compared with those from the other methods.The electronic transmission coefficient is calculated using the Landau Zener formalism.The slopes of the potential energy surfaces are directly obtained from the proposed accurate hydration functions.The coupling matrix element is calculated using the two state model and the numerical integral method over the the Slater type double zeta wave functions obtained using perturbation method.The theoretical value of the electron transfer rate and other parameters for V²⁺ （aq）/V³⁺ （aq）self exchange system are calculated and are compared with the corresponding experimental values.The applicability of the relevant models are also discussed.