Insight into the Mechanism of the Ru2+–Ru3+ Electron Self-Exchange Reaction from Quantitative Rate Calculations


  • This work was supported by an EPSRC First grant. J.B. acknowledges The Royal Society for a University Research Fellowship and a research grant. Simulations were carried out at the High Performance Computing Facilities “HECToR” (Edinburgh) and “Darwin” (University of Cambridge).


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The distance dependences of all electron-transfer parameters, including electronic coupling, were computed for the Ru2+–Ru3+ electron self-exchange reaction in aqueous solution. It was found that the probability for electron exchange is a maximum at a Ru2+–Ru3+ distance of 5.6 Å (see free-energy surface), which is significantly smaller than the envelopes of the [Ru(H2O)6]n+ complexes