Determining ab initio potential-dependent energetics is critical to the investigation of mechanisms for electrochemical reactions. While methodology for evaluating reaction thermodynamics is established, simulation techniques for the corresponding kinetics is still a major challenge owing to a lack of potential control, finite cell size effects, or computational expense. In this work, we develop a model that allows for computing electrochemical activation energies from just a handful of density functional theory (DFT) calculations. The sole input into the model are the atom-centered forces obtained from DFT calculations performed on a homogeneous grid composed of varying field strengths. We show that the activation energies as a function of the potential obtained from our model are consistent for different supercell sizes and proton concentrations for a range of electrochemical reactions.

中文翻译：

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确定电化学势垒中电位依赖性的基于力的方法

确定从头算电位依赖性能量学对于研究电化学反应机制至关重要。虽然建立了评估反应热力学的方法，但由于缺乏潜在的控制、有限的单元尺寸效应或计算费用，相应动力学的模拟技术仍然是一项重大挑战。在这项工作中，我们开发了一个模型，该模型允许仅通过少量密度泛函理论 (DFT) 计算来计算电化学活化能。模型的唯一输入是从由不同场强组成的均匀网格上执行的 DFT 计算获得的原子中心力。