title: Reactive trajectories of the Ru2+/3+self-exchange reaction and the connection to Marcus' theory.
abstract: Outer sphere electron transfer between two ions in aqueous solution is a rare event on the time scale of first principles molecular dynamics simulations. We have used transition path sampling to generate an ensemble of reactive trajectories of the self-exchange reaction between a pair of Ru2+and Ru3+ions in water. To distinguish between the reactant and product states, we use as an order parameter the position of the maximally localised Wannier center associated with the transferring electron. This allows us to align the trajectories with respect to the moment of barrier crossing and compute statistical averages over the path ensemble. We compare our order parameter with two typical reaction coordinates used in applications of Marcus theory of electron transfer: the vertical gap energy and the solvent electrostatic potential at the ions.
authors.affiliation: Van't Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands. b.ensing@uva.nl and Amsterdam Center for Multiscale Modeling, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Ambuj
authors.initials: A
authors.lastname: Tiwari
authors.affiliation: Van't Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands. b.ensing@uva.nl and Amsterdam Center for Multiscale Modeling, Science Park 904, 1098 XH Amsterdam, The Netherlands and Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain.
authors.forename: Bernd
authors.initials: B
authors.lastname: Ensing