Addition to “Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H 2 Evolution on Pt”
Addition to “Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H 2 Evolution on Pt”
复制标题
添加到“Pt 上 H 2 演化电化学能垒的恒电位隐式溶剂化计算评估”
DOI：
10.1021/acs.jpcc.9b05026
复制
发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Jónsson, Hannes
中科院分区：
文献类型：
--
作者：
Van den Bossche, Maxime;Skúlason, Egill;Rose-Petruck, Christoph;Jónsson, Hannes
在审查我们的文章期间，Richard Hennig 博士发布了一条消息 1，内容涉及当前 VASPsol 释放中总能量的缺失。所需的校正相当于 QV，其中 Q 是 DFT 子系统的净电荷，V 是本体溶剂中静电势的负值。我们确认，进行此校正后，计算出的活化能变得与 1/Lz 无关，并且与我们文章中报告的值非常一致，这些值是通过外推到 1/Lz= 0 获得的，无需进行能量校正。这种等价意味着所需的电势位移 V 也与 1/Lz 成比例，因此 QV 在大 Lz 的极限内接近于零。因此，如果总能量通过 QV 增加，则 1/Lz 外推方案是不必要的。
During the review of our article, a message was posted by Dr. Richard Hennig 1 concerning a missing contribution to the total energy in the present VASPsol release. The required correction amounts to QV with Q the net charge of the DFT subsystem and V the negative of the electrostatic potential in the bulk solvent. We confirm that, after making this correction, the calculated activation energies become independent of 1/Lz and closely agree with the values reported in our article, which were obtained via extrapolation to 1/Lz= 0 without the energy correction. This equivalence implies that the required potential shifts V are also proportional to 1/Lz and hence QV approaches zero in the limit of large Lz. The 1/Lz extrapolation scheme is therefore unnecessary provided that the total energies are augmented by QV.