Abstract 2-mercaptobenzothiazole (MBT) is known as an efficient corrosion inhibitor for copper. In the present work, we performed quantum chemical DFT calculations of the interaction of MBT on Cu(111) surfaces covered by an ultrathin Cu2O(111) film, in order to bring atomic scale insight on the corrosion inhibition properties of MBT on oxidized copper surfaces. Thione and thiolate forms of MBT are found to interact strongly with the oxidized surfaces. The formation of a monolayer at full coverage is favored over single molecular adsorption at low coverage with the molecules adopting a perpendicular orientation. Thione binds strongly via covalent bonding between the exocyclic sulfur atom and the under coordinated Cu site, and additional H-bonding between the NH group and surface oxygen atoms (NH…O H-bond). Thiolate binds more strongly via a second covalent bond between the N atom and saturated Cu site. Bonding interaction is confirmed by the electronic structure analysis and charge transfer. The adsorption process leads to the reconstruction of the topmost oxide surface. The calculations suggest that both forms of MBT may substitute H2O and OH at the Cu2O film surface, and thus may form a protective layer on oxidized copper surfaces in aqueous environment.

中文翻译：

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模型氧化铜表面 2-巯基苯并噻唑吸附的 DFT 研究及其与缓蚀的关系

摘要 2-巯基苯并噻唑（MBT）是一种有效的铜缓蚀剂。在目前的工作中，我们对超薄 Cu2O(111) 薄膜覆盖的 Cu(111) 表面上 MBT 的相互作用进行了量子化学 DFT 计算，以便从原子尺度上了解 MBT 在氧化铜表面上的腐蚀抑制性能. 发现硫酮和硫醇盐形式的 MBT 与氧化表面强烈相互作用。与分子采用垂直取向的低覆盖率下的单分子吸附相比，在全覆盖下形成单层更有利于形成。硫酮通过环外硫原子和下配位的 Cu 位点之间的共价键以及 NH 基团和表面氧原子之间的额外 H 键（NH ... O H 键）牢固结合。硫醇盐通过 N 原子和饱和 Cu 位点之间的第二个共价键更牢固地结合。电子结构分析和电荷转移证实了键合相互作用。吸附过程导致最上层氧化物表面的重建。计算表明，两种形式的 MBT 都可以替代 Cu2O 膜表面的 H2O 和 OH，因此可以在水性环境中的氧化铜表面形成保护层。