title: Density functional reactivity theory characterizes charge separation propensity in proton-coupled electron transfer reactions.
abstract: Proton-coupled electron transfer (PCET) reactions occur in many biological and artificial solar energy conversion processes. In these reactions the electron is often transferred to a site distant to the proton acceptor site. In this work, we employ the dual descriptor and the electrophilic Fukui function from density functional reactivity theory (DFRT) to characterize the propensity for an electron to be transferred to a site other than the proton acceptor site. The electrophilic regions of hydrogen bond or van der Waal reactant complexes were examined using these DFRT descriptors to determine the region of space to which the electron is most likely to be transferred. This analysis shows that in PCET reactions the electrophilic region of the reactant complex does not include the proton acceptor site.
authors.affiliation: Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, United States. shubin@email.unc.edu
authors.forename: Shubin
authors.initials: S
authors.lastname: Liu
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Ess
authors.forename: Cynthia K
authors.initials: CK
authors.lastname: Schauer
mesh_terms: D004583:Electrons; D006860:Hydrogen Bonding; D011522:Protons; D011789:Quantum Theory
chemical_list: D011522:Protons