Probing the role of surface termination in the adsorption of azupyrene on copper
Probing the role of surface termination in the adsorption of azupyrene on copper
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DOI：
10.1039/d3nr04690g
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发表时间：
2024-02-26
期刊：
影响因子：
6.7
通讯作者：
Duncan，David A.
中科院分区：
文献类型：
--
作者：
Klein，Benedikt P.;Stoodley，Matthew A.;Duncan，David A.
在有机-无机界面中，无机基质终止的作用对于包含强局部键合的系统已经得到了很好的研究。然而，如何改变基板终止影响协调离域电子状态，如发现在芳香族分子，是一个悬而未决的问题。Azupyrene是一种非交替的多环芳烃，已知通过其离域π轨道与金属表面强烈结合，从而产生离域表面-吸附物相互作用的理想探针。采用正入射X射线驻波（NIXSW）测量和密度泛函理论计算方法，研究了铜（111）、（110）和（100）表面晶面对蓝芘吸附结构的影响.基于混合密度泛函理论计算的结构模型与非局部多体色散产生良好的协议与实验NIXSW的结果。在（111）和（100）表面之间没有观察到统计学上显著的氮芘吸附高度差异。在Cu（110）表面上，发现该分子比在其他表面小面上更靠近衬底吸附0.06 ± 0.04 μ m。在每个表面上的最积极有利的吸附位点，由DFT确定，是微妙的不同，但在每种情况下涉及的配置，其中芳环的中心以上的空心网站，与以前的报告一致的吸附小芳香族分子在金属表面上。
The role of the inorganic substrate termination, within the organic–inorganic interface, has been well studied for systems that contain strong localised bonding. However, how varying the substrate termination affects coordination to delocalised electronic states, like that found in aromatic molecules, is an open question. Azupyrene, a non-alternant polycyclic aromatic hydrocarbon, is known to bind strongly to metal surfaces through its delocalised π orbitals, thus yielding an ideal probe into delocalised surface-adsorbate interactions. Normal incidence X-ray standing wave (NIXSW) measurements and density functional theory calculations are reported for the adsorption of azupyrene on the (111), (110) and (100) surface facets of copper to investigate the dependence of the adsorption structure on the substrate termination. Structural models based on hybrid density functional theory calculations with non-local many-body dispersion yield excellent agreement with the experimental NIXSW results. No statistically significant difference in the azupyrene adsorption height was observed between the (111) and (100) surfaces. On the Cu(110) surface, the molecule was found to adsorb 0.06 ± 0.04 Å closer to the substrate than on the other surface facets. The most energetically favoured adsorption site on each surface, as determined by DFT, is subtly different, but in each case involved a configuration where the aromatic rings were centred above a hollow site, consistent with previous reports for the adsorption of small aromatic molecules on metal surfaces.