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Journal of Electroanalytical Chemistry, Vol.829, 1-6, 2018
Spatial averaging of electrostatic potential differences in layered nanostructures with ionic hopping conductivity
Laws of spatial averaging on nanoscale for local electrostatic potential differences in ionic conductors are of key importance for the understanding of ion-transport phenomena and effects in space-charge layers. Currently, these laws are not investigated. As a consequence, the leading software packages for nanoscience do not have any competence for modeling of space-charge formation/relaxation in nanostructures with ionic hopping conductivity. So the article addresses the theme. For a layered nanostructure {X-k}, formed by parallel crystallographic X-k planes, an average electrostatic potential difference (< V-k,V-k+1 >) in a non-uniform field is defined in terms of normalized sums Sigma of the local works W-k,W-k+1 for X-k -> Xk+1 transitions of mobile ions in a field of a single point charge. At a weak external electrical influence on {X-k}, the < V-k,V-k+1 > can be easily generalized for a non-uniform field created by a set of point charges. The sums Sigma W(k,k+1 )are calculated for small average distances (similar to 0.6 nm) between mobile ions (as in advanced superionic conductors). Computer experiments show: (i) Sigma W-k,W-k+1 sums are independent of k-indices with the accuracy similar to 10%, (ii) probability density functions for local potential differences V-k,V-k+1 are close to normal distributions and (iii) < V-k,V-k+1 > approximate to V-k,k+1(U) where V-k,k+1(U) is a potential difference in a uniform electrostatic field. These nanoscale laws allow manipulating by an average potential difference (< V-k,V-k+N >) between X-k and Xk+N planes (N > 1), so the modeling of non-stationary ion-transport processes and energy flows in parallel combinations of nanostructures become possible.
Keywords:Average electrostatic potential difference;Solid electrolytes;Advanced superionic conductors;Nanostructures;Nanoionics;Modeling and simulations