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Volume 195, 2016
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Reactive trajectories of the Ru2+/3+ self-exchange reaction and the connection to Marcus' theory

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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.

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Publication details

The article was received on 11 May 2016, accepted on 15 Jun 2016 and first published on 05 Oct 2016


Article type: Paper
DOI: 10.1039/C6FD00132G
Citation: Faraday Discuss., 2016,195, 291-310
  • Open access: Creative Commons BY-NC license
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    Reactive trajectories of the Ru2+/3+ self-exchange reaction and the connection to Marcus' theory

    A. Tiwari and B. Ensing, Faraday Discuss., 2016, 195, 291
    DOI: 10.1039/C6FD00132G

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