Theory of proton coupled electron transfer reactions: Assessing the Born-Oppenheimer approximation for the proton motion using an analytically solvable model

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.

Graphical abstractAn analytically solvable model was employed to study proton coupled electron transfer reactions. Approximated theories are assessed, and vibrational coherence is observed in case of small reorganization energy.Download full-size imageResearch highlights► The Duschinsky rotation effect in PCET reactions. ► Assessment of the BO approx. for proton motion using an analytically solvable model. ► Vibrational coherence in PCET in the case of small reorganization energy.