2010/07/22 by Ren‐Hui Zheng, Renhui Zheng, Yuanyuan Jing +2
Biochemistry, Genetics and Molecular Biology · Chemistry · Physics and Astronomy · #Atomic physics #Born approximation #Born–Oppenheimer approximation #Chemistry #Deuterium #Electron #Electron Spin Resonance Studies #Electron transfer #Kinetic energy #Kinetic isotope effect #Kinetics #Marcus theory #Molecule #Photochemistry and Electron Transfer Studies #Photosynthetic Processes and Mechanisms #Physical chemistry #Physics #Proton #Proton-coupled electron transfer #Quantum mechanics #Quantum tunnelling #Range (aeronautics) #Reaction rate constant #Transfer (computing) #physics.chem-ph
paper · pdf · doi:10.1016/j.chemphys.2010.11.001
arxiv created 2010/07/22 · openalex publication_date 2010/11/12 · arxiv updated 2015/05/19 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/05
By employing an analytically solvable model including the Duschinsky rotation effect, we investigated the applicability of the commonly used Born-Oppenheimer (BO) approximation for separating the proton and proton donor-acceptor motions in theories of proton coupled electron transfer (PCET) reactions. Comparison with theories based on the BO approximation shows that, the BO approximation for the proton coordinate is generally valid while some further approximations may become inaccurate in certain range of parameters. We have also investigated the effect of vibrationally coherent tunneling in the case of small reorganization energy, and shown that it plays an important role on the rate constant and kinetic isotope effect.