Department of Chemistry , University of Rochester , 120 Trustee Road , Rochester , New York 14627 , United States.
J Phys Chem A. 2019 Mar 28;123(12):2470-2482. doi: 10.1021/acs.jpca.9b00077. Epub 2019 Mar 12.
We apply a recently developed quasi-diabatic (QD) propagation scheme to simulate proton-coupled electron transfer (PCET) reactions. This scheme enables a direct interface between an accurate diabatic dynamics approach and the adiabatic vibronic states of the coupled electron-proton subsystem. It explicitly avoids theoretical efforts to preconstruct diabatic states for the transferring electron and proton or reformulate a diabatic dynamics method to the adiabatic representation, both of which are nontrivial tasks. Using a partial linearized path-integral approach and symmetrical quasi-classical approach as the diabatic dynamics methods, we demonstrate that the QD propagation scheme provides accurate vibronic dynamics of PCET reactions and reliably predicts the correct reaction mechanism without any a priori assumptions. This work demonstrates the possibility to directly simulate challenging PCET reactions by using accurate diabatic dynamics approaches and adiabatic vibronic information.
我们应用最近开发的准非绝热（QD）传播方案来模拟质子耦合电子转移（PCET）反应。该方案在精确的非绝热动力学方法和耦合电子-质子子系统的绝热振子态之间实现了直接接口。它明确避免了为转移电子和质子预先构建非绝热态或重新表述非绝热动力学方法到绝热表示的理论工作，这两者都是非常困难的任务。我们使用部分线性化路径积分方法和对称准经典方法作为非绝热动力学方法，证明 QD 传播方案提供了 PCET 反应的准确振子动力学，并在没有任何先验假设的情况下可靠地预测了正确的反应机制。这项工作表明，通过使用精确的非绝热动力学方法和绝热振子信息，可以直接模拟具有挑战性的 PCET 反应。
