Journal Article10.1063/1.1744305
Adiabatic Rate Processes at Electrodes. I. Energy-Charge Relationships
784
TL;DR: In this article, the role of the dielectric in determining the course of thermally activated reactions is discussed, and a general interpretation of the transfer coefficient and an account of the activation process in simple systems are given in terms of the distribution of electron charge density in the transition state; these are shown to be in good accord with experiment.
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Abstract: The distinction between adiabatic and nonadiabatic reaction mechanisms at an electrode/solution interface is emphasized; in general, only adiabatic or near‐adiabatic paths are important in thermally activated reactions. The role of the dielectric in determining the course of such reactions is discussed. A general interpretation of the transfer coefficient and an account of the activation process in simple systems are given in terms of the distribution of electron charge density in the transition state; these are shown to be in good accord with experiment. The conventional approach to these problems, in which an approximate potential‐energy path for the reaction is calculated from intersecting potential‐energy curves for the initial and final states of the system, is criticized, and an alternative representation in terms of charge variation is proposed.
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References
A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions
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TL;DR: In this paper, the spectral and x-ray properties of water and ionic solutions have been deduced quantitatively in good agreement with experiment using a model of the water molecule derived from spectral and X-ray data.
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The colours and magnetic properties of hydrated iron group salts, and evidence for covalent bonding
TL;DR: In this paper, the authors analyzed the optical absorption data of paramagnetic salts containing [M(H 2 O)$O)$\6}, M = 3d$n}, and showed that the orbital level separations given by the optical spectrum are smaller than those predicted from magnetic data.
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