CO adsorption on Cu(100), (110), and (111) surfaces has been extensively studied using Kohn–Sham density functional theory calculations. A holistic analysis of adsorption energies, charge transfer, and structural changes has been employed to highlight the variations in adsorption mechanisms upon changing the surface type and the adsorption site. Each surface, with its unique arrangement of atoms, resulted in a varying adsorbate behavior, although the same adsorption site is considered. This directly reflects the influence of the atomic arrangement on the substrate–adsorbate interactions. Site-interactions are rigorously investigated using molecular-orbital and charge transfer principles taking into account the fundamental interaction of frontier (5σ and 2π*) orbitals. Considering the effects of the surface atomic arrangement and density of metal interacting orbitals, along with the relative d-5σ and d-2π* energy spacings, the calculated adsorption preference to higher coordination sites is explained, which also revealed valuable interpretations to the well-known DFT CO adsorption puzzle. In addition, we studied the perturbations occurring upon adsorption to the 3σ and 1π orbitals, which hold the internal C–O bond. Studying 3σ and 1π orbital perturbations provided a wealth of theoretical interpretations for the varying behavior of the adsorbate molecule when similar adsorption sites are compared at different facets.

中文翻译：

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揭露在铜表面的一氧化碳吸附：分子轨道原理的新见解†

使用Kohn-Sham密度泛函理论计算，已广泛研究了CO在Cu（100），（110）和（111）表面上的吸附。吸附能，电荷转移和结构变化的整体分析已被用来强调在改变表面类型和吸附位置时吸附机理的变化。尽管考虑了相同的吸附位点，但每个表面具有独特的原子排列方式，导致了不同的吸附物行为。这直接反映了原子排列对底物与被吸附物相互作用的影响。考虑到前沿（5σ和2π*）轨道的基本相互作用，使用分子轨道和电荷转移原理对位相互作用进行了严格的研究。考虑到表面原子排列和金属相互作用轨道的密度以及相对的d-5σ和d-2π*能量间隔的影响，解释了计算得到的对较高配位点的吸附偏好，这也为油井揭示了有价值的解释-已知的DFT CO吸附难题。另外，我们研究了吸附到3σ和1π轨道上的扰动，这些轨道具有内部C–O键。对3σ和1π轨道扰动的研究为在不同方面比较相似的吸附位点时吸附物分子的变化行为提供了丰富的理论解释。这也为著名的DFT CO吸附难题揭示了宝贵的解释。另外，我们研究了吸附到3σ和1π轨道上的扰动，这些轨道具有内部C–O键。对3σ和1π轨道扰动的研究为在不同方面比较相似的吸附位点时吸附物分子的变化行为提供了丰富的理论解释。这也为著名的DFT CO吸附难题揭示了宝贵的解释。另外，我们研究了吸附到3σ和1π轨道上的扰动，这些轨道具有内部C–O键。对3σ和1π轨道扰动的研究为在不同方面比较相似的吸附位点时吸附物分子的变化行为提供了丰富的理论解释。