Dependence of Vibronic Coupling on Molecular Geometry and Environment: Bridging Hydrogen Atom Transfer and Electron-Proton Transfer.

ABSTRACT: The rate constants for typical concerted proton-coupled electron transfer (PCET) reactions depend on the vibronic coupling between the diabatic reactant and product states. The form of the vibronic coupling is different for electronically adiabatic and nonadiabatic reactions, which are associated with hydrogen atom transfer (HAT) and electron-proton transfer (EPT) mechanisms, respectively. Most PCET rate constant expressions rely on the Condon approximation, which assumes that the vibronic coupling is independent of the nuclear coordinates of the solute and the solvent or protein. Herein we test the Condon approximation for PCET vibronic couplings. The dependence of the vibronic coupling on molecular geometry is investigated for an open and a stacked transition state geometry of the phenox

SUBMITTER: Harshan AK 

PROVIDER: S-EPMC4629534 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature