Abstract
The capabilities and limitations of the Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) for modeling proton coupled electron transfer (PCET) in the mixed-valence oxomanganese complex 1 [(bpy)(2)Mn(III)(mu-O)(2)Mn(IV)(bpy)(2)](3+) (bpy = 2,2'-bipyridyl) are analyzed. Complex 1 serves as a prototypical synthetic model for studies of redox processes analogous to those responsible for water oxidation in the oxygen-evolving complex (OEC) of photosystem II (PSII). DFT B3LYP free energy calculations of redox potentials and pKa's are obtained according to the thermodynamic cycle formalism applied in conjunction with a continuum solvation model. We find that the pKa's of the oxo-ligands depend strongly on the oxidation states of the complex, changing by approximately 10 pH units (i.e., from pH~2 to pH~12) upon III,IV-->III,III reduction of complex 1. These computational results are consistent with the experimental pKa's determined by solution magnetic susceptibility and near-IR spectroscopy as well as with the pH dependence of the redox potential reported by cyclic voltammogram measurements, suggesting that the III,IV-->III,III reduction of complex 1 is coupled to protonation of the di-mu-oxo bridge as follows: [(bpy)(2)Mn(III)(mu-O)(2) Mn(IV)(bpy)(2)](3+)+H(+)+e(-)-->[(bpy)(2)Mn(III)(mu-O)(mu-OH)Mn(III)(bpy)(2)](3+). It is thus natural to expect that analogous redox processes might strongly modulate the pKa's of oxo and hydroxo/water ligands in the OEC of PSII, leading to deprotonation of the OEC upon oxidation state transitions.