The Language of Electrochemistry

Abstract

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Lattice-gas models of adsorption in the double layer

“…Some previously studied models that can be defined by Eq. (1) or similar lattice-gas Hamiltonians, are the one for urea on Pt(100) [13,14,15,16,17,18,31], the model developed by Huckaby and Blum for UPD of copper on Au(111) in the presence of sulfate [6,7,8,9,19,20,32,33,34,35], and the standard three-state models with single-site bonding, used in previous studies of poisoning and enhancement in multicomponent adsorption [3,4,11,12,13]. As illustrations of the lattices and interactions that can be used, we show in Fig.…”

“…(1) are effective interactions mediated through several channels. The mechanisms involved include interactions between the adsorbate and the substrate electron structure [38,39,40,41,42], adsorbate-induced local deformations of the substrate, interactions with the fluid electrolyte [5,6,7,8,9,11,32,33,34,35], and (screened) electrostatic interactions [43]. All these effects give rise to indirect, effective interactions between the adsorbate particles.…”

“…In particular, the number of parameters that can reasonably be included in a lattice-gas model is large, and there is no a priori guarantee that a minimal set of fitted interactions is unique. Nevertheless, the encouraging results of previous lattice-gas studies of electrochemical systems that have employed this strategy [2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,32,33,34,35] indicate that when proper attention is paid to including all available experimental information in a consistent fashion, the predictive power of this approach is considerable. Furthermore, as effective interactions obtained by first-principles calculations become available in the future, the results obtained from latticegas models will provide crucial information for testing the consistency of such first-principles interactions with the experimentally observed thermodynamic and structural information.…”

“…At nonzero temperatures, the thermodynamic and structural properties of the lattice-gas model constructed through steps 1-3 can be studied by a number of analytical and numerical methods, depending on the quantities of interest and the complexity of the Hamiltonian. These methods include mean-field approximations [10,29] (although these can be unreliable for lowdimensional systems with short-range interactions [44]), Padé-approximant methods based on liquid theory [6,7,8,9,32,33,34,35], numerical TM calculations [2,3,4,11,12,13], and MC simulations [4,14,15,16,17,18,19,20]. 5.…”

“…In Sec. 4 we provide further quantitative illustrations in the form of applications to two specific cases of adsorption on single-crystal electrodes: the electrosorption of urea on Pt(100) from an acid electrolyte [13,14,15,16,17,18,31] and the underpotential deposition (UPD) of copper on Au(111) from a sulfate-containing electrolyte [6,7,8,9,19,20,32,33,34,35]. A final summary and conclusions are given in Sec.…”