Abstract
Abstract A model electrochemical ion-transfer reaction is investigated by molecular dynamics simulations. Non-equilibrium solvation effects can lead to barrier recrossings when the ion passes the transition state. The resulting transmission coefficient, which measures the deviation of the rate from the predictions of the transition state theory, is in good agreement with the Grote–Hynes theory. By contrast, Kramers theory predicts a much lower rate constant. The reaction occurs in the polarization caging regime of Grote–Hynes theory, in which the solvent motion controls the advance of the reaction. Furthermore, the molecular friction depends strongly on the distance from the electrode.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
