We investigate dispersion interactions in a selection of atomic, molecular, and molecule–surface systems, comparing high-level correlated methods with empirically corrected density functional theory (DFT). We assess the efficacy of functionals commonly used for surface-based calculations, with and without the D3 correction of Grimme. We find that the inclusion of the correction is essential to get meaningful results, but there is otherwise little to distinguish between the functionals. We also present coupled-cluster quality interaction curves for H₂, NO₂, H₂O, and Ar interacting with large carbon flakes, acting as models for graphene surfaces, using novel absolutely localized molecular orbital based methods. These calculations demonstrate that the problems with empirically corrected DFT when investigating dispersion appear to compound as the system size increases, with important implications for future computational studies of molecule–surface interactions.

中文翻译：

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小分子与石墨烯薄片之间分散相互作用的计算研究

我们研究了原子，分子和分子-表面系统选择中的色散相互作用，将高级相关方法与经验校正的密度泛函理论（DFT）进行了比较。我们评估使用和不使用Grimme进行D3校正时，通常用于基于表面的计算的功能的功效。我们发现，包含校正对于获得有意义的结果是必不可少的，但在其他方面几乎没有区别。我们还给出了H ₂，NO ₂，H _2的耦合簇质量相互作用曲线O和Ar与新颖的基于分子轨道的绝对局部化方法相互作用的大型碳薄片，充当石墨烯表面的模型。这些计算表明，当研究分散性时，凭经验校正的DFT的问题似乎随着系统尺寸的增加而变得复杂，这对未来分子-表面相互作用的计算研究具有重要意义。