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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Effects of Intrinsic Surface Defects on Thiophenol Self-Assembiy on Au(111): Surface Structures and Reaction Mechanisms
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Effects of Intrinsic Surface Defects on Thiophenol Self-Assembiy on Au(111): Surface Structures and Reaction Mechanisms

机译：内在表面缺陷对Au（111）上硫酚自组装的影响：表面结构和反应机理

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Density functional theory calculations were used to examine the effects of intrinsic surface defects of Au(111) on nondissociative thiophenol (PhSH) adsorption and the follow-up reaction pathways toward the dissociation of PhSH to form phenyl-thiolate (PhS) and then stable PhS adsorption structures. The calculations yielded the surface geometry of the most probable adsorption products, on Au(111) with and without the presence of adatoms (Au_(ad)) and vacancies, including the adsorption geometry of stable PhS-Au_(ad)-PhS surface complexes formed as the optimal products of dissociative adsorption toward the growth of a self-assembled monolayer of phenyl-thiolates. The validity of the computational adsorption geometries and our analysis of them are supported by the agreement between our simulated scanning tunneling microscopic images derived from these adsorption structures and the experimental images available in the literature. To elucidate further the adsorption reaction dynamics, we calculated the relevant reaction pathways and activation barriers and found that whereas the lowest energy barrier for the formation of the most stable PhS-PhS pair with the closest separation on clean Au(lll) with no intrinsic defects is 0.68 eV, the counterpart with Au_(ad) is only 0.32 eV. This and our other calculated results highlight the facilitating role of intrinsic defects of Au(lll) in driving the dissociative adsorption of thiophenol and articulate the reaction mechanism of the formation of the trans-PhS-Au_(ad)-PhS surface complex, which is the precursor to the final completion of a self-assembled monolayer of phenyl-thiols: the end product of thiophenol adsorption.
机译：密度泛函理论计算用于检验Au（111）固有表面缺陷对非解离性硫酚（PhSH）吸附的影响以及后续的反应途径，从而使PhSH解离形成苯基硫醇盐（PhS）然后形成稳定的PhS吸附结构。计算得出最有可能的吸附产物在Au（111）上存在和不存在吸附原子（Au_（ad））和空位时的表面几何形状，包括稳定的PhS-Au_（ad）-PhS表面复合物的吸附几何形状形成的最佳产物是解离吸附朝着硫醇盐自组装单层生长的最佳产物。由这些吸附结构得到的模拟扫描隧道显微图像与文献中提供的实验图像之间的一致性支持了计算吸附几何形状的有效性以及我们对它们的分析。为了进一步阐明吸附反应动力学，我们计算了相关的反应途径和活化障碍，并发现，形成最稳定的PhS-PhS对的最低能垒与在纯Au（III）上最接近的分离没有内在缺陷为0.68 eV，与Au_（ad）对应的仅为0.32 eV。该结果和我们的其他计算结果突出了Au（III）的固有缺陷在驱动硫酚解离吸附和阐明反式PhS-Au_（ad）-PhS表面复合物形成的反应机理方面的促进作用。苯硫醇自组装单层最终完成的前体：硫酚吸附的最终产物。

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