title: Substituent effects on the vibronic coupling for the phenoxyl/phenol self-exchange reaction.
abstract: The impact of substituents on the vibronic coupling for the phenoxyl/phenol self-exchange reaction, which occurs by a proton-coupled electron transfer mechanism, is investigated. The vibronic couplings are calculated with a grid-based nonadiabatic method and a nuclear-electronic orbital nonorthogonal configuration interaction method. The quantitative agreement between these two methods for the unsubstituted phenoxyl/phenol system and the qualitative agreement in the predicted trends for the substituted phenoxyl/phenol systems provides a level of validation for both methods. Analysis of the results indicates that electron-donating groups enhance the vibronic coupling, while electron-withdrawing groups attenuate the vibronic coupling. Thus, if all other aspects of the reaction are the same, then electron-donating groups will increase the rate, while electron-withdrawing groups will decrease the rate. Correlations between the vibronic coupling and physical properties of the phenol are also analyzed. Negative Hammett constants correspond to higher vibronic couplings, while positive Hammett constants correspond to similar or slightly lower vibronic couplings relative to the unsubstituted phenoxyl/phenol system. In addition, lower bond dissociation enthalpies, ionization potentials, and redox potentials, as well as higher pKa values, tend to correspond to higher vibronic couplings relative to the unsubstituted phenoxyl/phenol system. The observed trends enable the prediction of the impact of general substituents on the vibronic coupling, and hence the rate, for the phenoxyl/phenol self-exchange reaction. The fundamental physical insights obtained from these studies are applicable to other proton-coupled electron transfer systems.
authors.affiliation: Department of Chemistry, Pennsylvania State University, 104 Chemistry Building, University Park, Pennsylvania 16802, USA.
authors.forename: Michelle K
authors.initials: MK
authors.lastname: Ludlow
authors.forename: Jonathan H
authors.initials: JH
authors.lastname: Skone
authors.forename: Sharon
authors.initials: S
authors.lastname: Hammes-Schiffer
mesh_terms: D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D019800:Phenol / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*; D011522:Protons; D014732:Vibration
chemical_list: D010636:Phenols; D011522:Protons; C042329:phenoxy radical; D019800:Phenol; D010100:Oxygen