title: Proton-Coupled Electron Transfer: Moving Together and Charging Forward.
abstract: Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa's for molecular electrocatalysts, as well as insights into linear correlations and non-innocent ligands, are also described. In addition, computational methods for simulating the nonadiabatic dynamics of photoexcited PCET are discussed. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Sharon
authors.initials: S
authors.lastname: Hammes-Schiffer
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000737:chemistry; D040761:Biomimetic Materials / Q000737:chemistry*; D032701:Biomimetics; D002384:Catalysis; D003198:Computer Simulation; D004563:Electrochemistry; D004579:Electron Transport; D004583:Electrons; D006864:Hydrogenase / Q000737:chemistry*; D007700:Kinetics; D008084:Lipoxygenase / Q000737:chemistry*; D008954:Models, Biological; D008956:Models, Chemical; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D011522:Protons; D013025:Glycine max / Q000737:chemistry / Q000201:enzymology*; D013816:Thermodynamics
chemical_list: D009942:Organometallic Compounds; D011522:Protons; C103599:bis(bipyridyl)ruthenium(II); C556179:cobaloxime; D015082:2,2'-Dipyridyl; D006864:Hydrogenase; D008084:Lipoxygenase