%0 Journal Article
%A Xiaohui Qu
%A Kristin A Persson
%B Journal of Chemical Theory and Computation
%D 2016
%G eng
%N 9
%P 4501 - 4508
%R 10.1021/acs.jctc.6b00289
%T Toward Accurate Modeling of the Effect of Ion-Pair Formation on Solute Redox Potential
%V 12
%8 08/2016
%! J. Chem. Theory Comput.
%X <p><span>A scheme to model the dependence of a solute redox potential on the supporting electrolyte is proposed, and the results are compared to experimental observations and other reported theoretical models. An improved agreement with experiment is exhibited if the effect of the supporting electrolyte on the redox potential is modeled through a concentration change induced via ion pair formation with the salt, rather than by only considering the direct impact on the redox potential of the solute itself. To exemplify the approach, the scheme is applied to the concentration-dependent redox potential of select molecules proposed for nonaqueous flow batteries. However, the methodology is general and enables rational computational electrolyte design through tuning of the operating window of electrochemical systems by shifting the redox potential of its solutes; including potentially both salts as well as redox active molecules.</span></p>