Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches.
Solvation at metal/water interfaces: An ab initio molecular dynamics benchmark of common computational approaches.
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DOI：
10.26434/chemrxiv.11586363
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发表时间：
2020-01
期刊：
影响因子：
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通讯作者：
H. H. Heenen-H.;Joseph A. Gauthier;H. Kristoffersen;T. Ludwig;Karen Chan
中科院分区：
文献类型：
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作者：
H. H. Heenen-H.;Joseph A. Gauthier;H. Kristoffersen;T. Ludwig;Karen Chan
确定溶剂对电化学反应能量学的影响是我们理解电化学界面的一个核心挑战。到目前为止，还不清楚现有的方法如何预测固/液界面的溶剂化能，因为它们不能通过实验进行评估。从头算分子动力学（AIMD）模拟提出了一个物理上高度准确，但也是一个非常昂贵的方法。在这项工作中，我们采用广泛的AIMD模拟基准溶剂化在电荷中性金属/水界面对常用的连续溶剂模型。我们考虑了各种吸附物，包括 * CO，* CHO，* COH，* OCCHO，* OH，和 * OOH的铜，Au，和Pt面溶剂化的水。所考虑的表面和吸附物是相关的，除其他反应外，电化学CO2还原和氧的氧化还原反应。我们确定的方向氢键和空间位阻水的竞争是至关重要的正确的描述在金属/水界面的溶剂化。因此，我们发现，最常用的连续溶剂化方法，尚未捕获这些属性，目前不提供更准确的能量在真空中的模拟。我们发现大多数计算的基准溶剂化能与氢键或竞争性水吸附成线性比例，这在表面上有很大的不同。因此，我们确定的溶剂化能的吸附是不可转移的金属表面之间，在标准的做法。
Determining the influence of the solvent on electrochemical reaction energetics is a central challenge in our understanding of electrochemical interfaces. To date, it is unclear how well existing methods predict solvation energies at solid/liquid interfaces, since they cannot be assessed experimentally. Ab initio molecular dynamics (AIMD) simulations present a physically highly accurate, but also a very costly approach. In this work, we employ extensive AIMD simulations to benchmark solvation at charge-neutral metal/water interfaces against commonly applied continuum solvent models. We consider a variety of adsorbates including *CO, *CHO, *COH, *OCCHO, *OH, and *OOH on Cu, Au, and Pt facets solvated by water. The surfaces and adsorbates considered are relevant, among other reactions, to electrochemical CO2 reduction and the oxygen redox reactions. We determine directional hydrogen bonds and steric water competition to be critical for a correct description of solvation at the metal/water interfaces. As a consequence, we find that the most frequently applied continuum solvation methods, which do not yet capture these properties, do not presently provide more accurate energetics over simulations in vacuum. We find most of the computed benchmark solvation energies to linearly scale with hydrogen bonding or competitive water adsorption, which strongly differ across surfaces. Thus, we determine solvation energies of adsorbates to be non-transferable between metal surfaces, in contrast to standard practice.