Han Yu, Li Xiao-Yan, Zhu Beien, Gao Yi
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2022 Sep 22;126(37):6538-6547. doi: 10.1021/acs.jpca.2c03124. Epub 2022 Sep 13.
Surface reconstruction changes the atomic configuration of the metal surface and thus alters its intrinsic physical and chemical properties. Recent in situ experiments have shown a variety of surface reconstructions under reaction conditions, but how to effectively predict and characterize these structures remains challenging. Herein, we combine a DFT-based kinetic Monte Carlo simulation method and ab initio thermodynamics to explore the low-energy configurations of metal surface reconstructions, which takes the surface dynamics under the reactive environment into account. We systematically simulate 13 Au surfaces ((100), (110), (111), (210), (211), (221), (310), (311), (320), (321), (322), (331), and (332)) in the CO environment and identify 19 candidate reconstruction patterns driven by CO adsorption. The breakup of the original surfaces is attributed to the lateral interactions among the nearest-neighboring adsorbates. This work provides an efficient approach to unveil the reconstructed metal surface structures in reactive environments for guiding the experiments.
表面重构改变了金属表面的原子构型，从而改变了其固有的物理和化学性质。最近的原位实验表明，在反应条件下存在多种表面重构情况，但如何有效地预测和表征这些结构仍然具有挑战性。在此，我们结合基于密度泛函理论（DFT）的动力学蒙特卡罗模拟方法和第一性原理热力学，来探索金属表面重构的低能量构型，该方法考虑了反应环境下的表面动力学。我们系统地模拟了13个金表面（(100)、(110)、(111)、(210)、(211)、(221)、(310)、(311)、(320)、(321)、(322)、(331)和(332)）在CO环境中的情况，并确定了由CO吸附驱动的19种候选重构模式。原始表面的破裂归因于最近邻吸附质之间的横向相互作用。这项工作提供了一种有效的方法来揭示反应环境中重构的金属表面结构，以指导实验。
