Abstract Using density functional theory we explore the adsorption of pyridine (NC5H5) on Cu, Ag, and Au(111) surfaces. To study the effect of coverage we run calculations on a 3 × 4 (12 atom), 4 × 4 (16 atom), 5 × 4 (20 atom), and 4 × 6 (24 atom) surface. To examine the role of the van der Waals interaction we use the following vdW inclusive functionals: optB86-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, rPW86-vdW2, SCAN+rVV10 along with the PBE functional. Regardless of functional, metal, and coverage we find the most energetically stable adsorption site to be a vertical site with the pyridine's N atom directly above a metal atom, which contradicts the available experimental literature. Introducing the vdW interaction lowers the energy gap between the most energetically favorable flat and vertical adsorption configurations. Moving to a higher coverage increases the overall interaction of the pyridine molecule with the surface. We also find that the SCAN+rVV10 functional performs similarly to the optB86b-vdW and optB88-vdW functional. Along with the geometric properties of the substrate/adsorbate system, we report several electronic properties of the substrate/adsorbate system such as charge transfer from the surface to the molecule, change in the surface's work function, and change in d-band of the atoms in the first layer of the substrate.

中文翻译：

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吡啶在 (111) 铸币金属表面吸附的覆盖率相关研究

摘要 利用密度泛函理论，我们探索了吡啶 (NC5H5) 在 Cu、Ag 和 Au(111) 表面上的吸附。为了研究覆盖率的影响，我们在 3 × 4（12 原子）、4 × 4（16 原子）、5 × 4（20 原子）和 4 × 6（24 原子）表面上运行计算。为了检查范德华相互作用的作用，我们使用以下包含 vdW 的功能：optB86-vdW、optB88-vdW、optPBE-vdW、revPBE-vdW、rPW86-vdW2、SCAN+rVV10 以及 PBE 功能。无论功能、金属和覆盖范围如何，我们发现能量最稳定的吸附位点是吡啶的 N 原子直接位于金属原子上方的垂直位点，这与可用的实验文献相矛盾。引入 vdW 相互作用降低了最有利的平面和垂直吸附配置之间的能隙。移动到更高的覆盖范围会增加吡啶分子与表面的整体相互作用。我们还发现 SCAN+rVV10 函数的性能与 optB86b-vdW 和 optB88-vdW 函数相似。除了底物/吸附物系统的几何特性外，我们还报告了底物/吸附物系统的几种电子特性，例如从表面到分子的电荷转移、表面功函数的变化以及原子 d 带的变化在基板的第一层。