Electrochemical Barriers Made Simple
Electrochemical Barriers Made Simple
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DOI：
10.1021/acs.jpclett.5b01043
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发表时间：
2015-07-16
影响因子：
5.7
通讯作者：
Norskov, Jens K.
中科院分区：
文献类型：
--
作者：
Chan, Karen;Norskov, Jens K.
电化学电荷转移势垒的理论处理中的一个主要挑战是在恒定电荷下进行模拟，这导致沿着反应路径的显著电势变化。然而，真实的电化学系统在恒定电势下操作，这对应于无限大小的假设模型系统。以前的析氢研究依赖于计算成本高的方案，该方案外推在越来越大的电池上计算的势垒，并且将该方案扩展到更复杂的反应将是昂贵的。我们提出了一种新的方法来确定简单的电荷转移反应的恒电位反应能量，只需要（1）在电化学环境中的单势垒计算和（2）在初始，过渡和最终状态的相应的表面电荷。这种方法允许在所需的计算资源，以确定电化学障碍，并铺平了道路，严格的DFT为基础的动力学分析的电化学反应超出析氢的巨大减少。
A major challenge in the theoretical treatment of electrochemical charge transfer barriers is that simulations are performed at constant charge, which leads to dramatic potential shifts along the reaction path. Real electrochemical systems, however, operate at constant potential, which corresponds to a hypothetical model system of infinite size. Previous studies of hydrogen evolution have relied on a computationally costly scheme that extrapolates the barriers calculated on increasingly larger cells, and extension of this scheme to more complex reactions would be prohibitively costly. We present a new method to determine constant potential reaction energetics for simple charge transfer reactions that requires only (1) a single barrier calculation in an electrochemical environment and (2) the corresponding surface charge at the initial, transition, and final states. This method allows for a tremendous reduction in the computational resources required to determine electrochemical barriers and paves the way for a rigorous DFT-based kinetic analysis of electrochemical reactions beyond hydrogen evolution.