Marcus Theory of Ion-Pairing

• Published in: Journal of chemical theory and computation Vol. 13; no. 8; pp. 3470 - 3477
• Main Authors: Roy, Santanu, Baer, Marcel D, Mundy, Christopher J, Schenter, Gregory K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.08.2017
• Subjects: Biological activity; Computer simulation; Coordination numbers; Correlation analysis; Electron transfer; Ion pairs; Ions; Molecular chains; Molecular dynamics; Reaction kinetics; Water chemistry
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.7b00332

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 2D surfaces computed from molecular dynamics simulations of different monovalent ion pairs reveal a Marcus-like mechanism for ion-pairing: Water molecules rearrange forming an activated coordination state prior to ion pair dissociation or association, followed by relaxation of the coordination state due to further water rearrangement. Like Marcus theory, we find the existence of an inverted region where the transition rates are slower with increasing exergonicity. This study provides a new perspective for the future investigations of ion-pairing and transport.