Wei Ziyang, Göltl Florian, Steinmann Stephan N, Sautet Philippe
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Department of Biosystems Engineering, The University of Arizona, Tucson, Arizona 85721, United States.
J Phys Chem Lett. 2022 Jul 7;13(26):6079-6084. doi: 10.1021/acs.jpclett.2c01376. Epub 2022 Jun 27.
Electrocatalysis plays a key role in sustainable energy conversion and storage. It is critical to model the grand canonical treatment of electrons, which accounts for the electrochemical potential explicitly, at the atomic scale and understand these reactions at electrified interfaces. However, such a grand canonical treatment for electrocatalytic modeling is in practice restricted to a treatment of electronic structure with density functional theory, and more accurate methods are in many cases desirable. Here, we develop an original workflow combining the grand canonical treatment of electrons with many-body perturbation theory in its random phase approximation (RPA). Using the potential dependent adsorption of carbon monoxide on the copper (100) facet, we show that the grand canonical RPA energetics provide the correct on-top Cu geometry for CO at reducing potential. The match with experimental results is significantly improved compared to the functionals at the generalized gradient approximation level, which is the most commonly used approximation for electrochemical applications. We expect this development to pave the way to further electrochemical applications using RPA.
电催化在可持续能源转换与存储中起着关键作用。在原子尺度上对电子的巨正则处理进行建模至关重要，这种处理明确考虑了电化学势，并理解带电界面处的这些反应。然而，这种用于电催化建模的巨正则处理在实践中仅限于用密度泛函理论处理电子结构，在许多情况下更精确的方法是可取的。在此，我们开发了一种原创的工作流程，将电子的巨正则处理与多体微扰理论的随机相位近似（RPA）相结合。利用一氧化碳在铜（100）晶面上的电位依赖吸附，我们表明巨正则RPA能量学为还原电位下的一氧化碳提供了正确的顶位铜几何结构。与广义梯度近似水平的泛函相比，与实验结果的匹配度显著提高，广义梯度近似是电化学应用中最常用的近似方法。我们期望这一进展为使用RPA的进一步电化学应用铺平道路。
