title: A three-step kinetic model for electrochemical charge transfer in the hopping regime.
abstract: Single-step nonadiabatic electron tunneling models are widely used to analyze electrochemical rates through self-assembled monolayer films (SAMs). For some systems, such as nucleic acids, long-range charge transfer can occur in a "hopping" regime that involves multiple charge transfer events and intermediate states. This report describes a three-step kinetic scheme to model charge transfer in this regime. Some of the features of the three-step model are probed experimentally by changing the chemical composition of the SAM. This work uses the three-step model and a temperature dependence of the charge transfer rate to extract the charge injection barrier for a SAM composed of a 10-mer peptide nucleic acid that operates in the hopping regime.
authors.affiliation: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
authors.forename: Xing
authors.initials: X
authors.lastname: Yin
authors.forename: Emil
authors.initials: E
authors.lastname: Wierzbinski
authors.forename: Hao
authors.initials: H
authors.lastname: Lu
authors.forename: Silvia
authors.initials: S
authors.lastname: Bezer
authors.forename: Arnie R
authors.initials: AR
authors.lastname: de Leon
authors.forename: Kathryn L
authors.initials: KL
authors.lastname: Davis
authors.forename: Catalina
authors.initials: C
authors.lastname: Achim
authors.forename: David H
authors.initials: DH
authors.lastname: Waldeck
mesh_terms: D000465:Algorithms; D003198:Computer Simulation; D004583:Electrons; D007700:Kinetics; D008956:Models, Chemical; D008957:Models, Genetic; D020135:Peptide Nucleic Acids / Q000737:chemistry*; D013696:Temperature
chemical_list: D020135:Peptide Nucleic Acids