We investigate the adsorption behavior of various molecules on black phosphorus (BP), employing molecular dynamics (MD)-based free energy calculations in combination with experimental measurements. We find a semiquantitative agreement between experiment and theory. Our approach works best at the low concentration limit, as this allows us to neglect adsorbate–adsorbate interactions, both in solution and on the surface. We also conducted simulations at high concentrations to qualitatively estimate these effects and propose a suitable isotherm model for adsorbates. Our results highlight the impact of molecular structure, shape, polarity, and the alignment of adsorbates relative to the BP surface along with the solvent environment on adsorption. Our approach uses generally available methods and can be extended to arbitrary organic molecules and solvents, potentially allowing for a high throughput screening of candidate molecules for noncovalent functionalization of BP.

中文翻译：

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黑磷的非共价功能化：自由能模拟与吸附实验


我们采用基于分子动力学 (MD) 的自由能计算并结合实验测量，研究了各种分子在黑磷 (BP) 上的吸附行为。我们发现实验和理论之间存在半定量的一致性。我们的方法在低浓度限制下效果最好，因为这使我们能够忽略溶液中和表面上的吸附物-吸附物相互作用。我们还进行了高浓度模拟，以定性估计这些影响，并提出合适的吸附物等温线模型。我们的结果强调了分子结构、形状、极性、吸附物相对于 BP 表面的排列以及溶剂环境对吸附的影响。我们的方法使用普遍可用的方法，并且可以扩展到任意有机分子和溶剂，有可能实现对 BP 非共价功能化候选分子的高通量筛选。