Marcus Theory of Ion-Pairing

摘要

We present a theory for ion pair dissociation and association, motivated by the concepts of Marcus theory of electron transfer. Despite the extensive research on ion pairing in many chemical and biological processes, much can be learned from the exploration of collective reaction coordinates. To this end, we explore two reaction coordinates, ion pair distance and coordination number. The study of the correlation between these reaction coordinates provides a new insight into the mechanism and kinetics of ion pair dissociation and association in water. The potential of mean force on these different monovalent ion pairs reveal a Marcus-like mechanism coordination state prior to ion pair dissociation or association, water rearrangement. Like Marcus theory, we find the existence increasing exergonicity. This study provides a new perspective 2D surfaces computed from molecular dynamics simulations of for ion-pairing: Water molecules rearrange forming an activated followed by relaxation of the coordination state due to further of an inverted region where the transition rates are slower with for the future investigations of ion-pairing and transport.