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Elsevier, Surface Science

DOI: 10.1016/j.susc.2016.03.022

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Repulsive Interactions Induced by Specific Adsorption: Anomalous Step Diffusivity and Inadequacy of Nearest-Neighbor Ising Model (Part II Theory)

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Abstract

This is Part II of two closely related papers, where we show that the strong repulsive interaction caused by specifically adsorbed anions leads to a failure of the nearest-neighbor Ising model to describe structures on electrode surfaces. In this part, an analytical form of the step diffusivity is derived in terms of nearest and next-nearest neighbor interactions for steps with a mean direction along 〈110〉 (the close-packed direction). With the help of a further analytical expression for the diffusivity of steps with 〈100〉 mean orientation a simple scheme is developed whereby the nearest and next-nearest interaction energies can be extracted from the experimental values for the diffusivity along the 〈110〉 - and 〈100〉-directions. The method is applicable to repulsive and attractive next-nearest neighbor interactions, both for surfaces in vacuum and in contact with an electrolyte. An example is presented in Part I, where we apply our approach to Au(100) in Br--, Cl-- and SO42—containing electrolytes.