Potential Dependence of Electrochemical Barriers from ab Initio Calculations
Potential Dependence of Electrochemical Barriers from ab Initio Calculations
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DOI：
10.1021/acs.jpclett.6b00382
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发表时间：
2016-05-05
影响因子：
5.7
通讯作者：
Norskov, Jens K.
中科院分区：
文献类型：
--
作者：
Chant, Karen;Norskov, Jens K.
我们提出了一个简单的和计算有效的方法来确定潜在的依赖性的质子-电子转移的激活能从一个单一的从头计算势垒计算。我们表明，潜在的依赖性的活化能给出的部分电荷转移在过渡态。该方法进行评估，对明确确定的潜在的依赖性，通过多次计算在不同的电位。我们表明，转移系数是由从初始过渡态，这对电化学动力学具有重要意义的电荷转移。
We present a simple and computationally efficient method to determine the potential dependence of the activation energies for proton-electron transfer from a single ab initio barrier calculation. We show that the potential dependence of the activation energy is given by the partial charge transferred at the transition state. The method is evaluated against the potential dependence determined explicitly through multiple calculations at varying potential. We show that the transfer coefficient is given by the charge transferred from the initial to transition state, which has significant implications for electrochemical kinetics.