Activation energy of electrode reactions: the non-local effects
作者： P.G. Dzhavakhidze , A.A. Kornyshev , L.I. Krishtalik
DOI: 10.1016/0022-0728(87)80115-8
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摘要: We present the first results on effect of spatial dispersion solvent dielectric permittivity and field penetration into a metal kinetic parameters heterogenous electron-transfer reactions. The calculation is based rough but exactly solvable “sharp boundary model” interface. obtained differ substantially from those given by Marcus theory (in which these effects are neglected) both in absolute values dependence calculated distance between reactant electrode. In particular, we arrive at decrease activation energy with increase electrode-reactant separation. This phenomenon changes conclusions about an optimal electron transfer: it might ion closest approach to electrode turn out be strongly solvent-dependent. violation relationship reorganization heterogeneous homogeneous reactions some other problems discussed light new results.
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