DFT study of gas-phase adsorption of benzotriazole on Cu(111), Cu(100), Cu(110), and low coordinated defects thereon.
DFT study of gas-phase adsorption of benzotriazole on Cu(111), Cu(100), Cu(110), and low coordinated defects thereon.
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DOI：
10.1039/c1cp21873e
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发表时间：
2011-11
期刊：
影响因子：
--
通讯作者：
Sebastijan Peljhan;A. Kokalj
中科院分区：
文献类型：
--
作者：
Sebastijan Peljhan;A. Kokalj
采用密度泛函理论（DFT）研究了苯并三氮唑在Cu（111）、Cu（100）、Cu（110）及其配位缺陷上的吸附行为.我们发现，苯并三氮唑可以化学吸附在一个直立的几何形状或物理吸附的分子平面几乎平行于表面。虽然化学吸附能的大小随着从密集堆积的Cu（111）到更开放的表面和低配位缺陷而增加，但物理吸附能在所有三个低米勒指数表面上相当相似。指出由于苯并三氮唑的偶极矩较大，偶极间的相互作用是相当重要的。对于垂直的化学吸附模式的横向排斥是非常长的范围内，延伸到最近的邻居距离约60玻尔，而平行的吸附模式的横向相互作用是远远不太明显，分子的经验，在距离为25玻尔弱吸引力。因此，通过最近开发的方案将化学吸附能外推到零覆盖，并且对于Cu（111）、Cu（100）和Cu（110），所得值分别为-0.60、-0.73和-0.92 eV，而零覆盖物理吸附能约为-0.7 eV，与表面平面无关。虽然更密集堆积的表面没有足够的反应性与分子π-系统相互作用，但Cu（110）的反应性似乎是在这种相互作用的开始，导致非常稳定的平行吸附结构，吸附能为-1.3 eV，这归因于表观化学吸附+物理吸附模式。
The adsorption of benzotriazole--an outstanding corrosion inhibitor for copper--on Cu(111), Cu(100), Cu(110), and low coordinated defects thereon has been studied and characterized using density functional theory (DFT) calculations. We find that benzotriazole can either chemisorb in an upright geometry or physisorb with the molecular plane being nearly parallel to the surface. While the magnitude of chemisorption energy increases as passing from densely packed Cu(111) to more open surfaces and low coordinated defects, the physisorption energy is instead rather similar on all three low Miller index surfaces. It is pointed out that due to a large dipole moment of benzotriazole the dipole-dipole interactions are rather important. For perpendicular chemisorption modes the lateral repulsion is very long ranged, extending up to the nearest-neighbor distance of about 60 bohrs, whereas for parallel adsorption modes the lateral interactions are far less pronounced and the molecules experience a weak attraction at distances ≲25 bohrs. The chemisorption energies were therefore extrapolated to zero coverage by a recently developed scheme and the resulting values are -0.60, -0.73, and -0.92 eV for Cu(111), Cu(100), and Cu(110), respectively, whereas the zero-coverage physisorption energy is about -0.7 eV irrespective of the surface plane. While the more densely packed surfaces are not reactive enough to interact with the molecular π-system, the reactivity of Cu(110) appears to be at the onset of such interaction, resulting in a very stable parallel adsorption structure with an adsorption energy of -1.3 eV that is ascribed as an apparent chemisorption+physisorption mode.