Abstract Chemical reactions on surfaces play central roles in heterogeneous catalysis, and most reactions involve the formation and/or the cleavage of bonds. At present, density functional theory (DFT) has become the workhorse for computational investigation of reaction mechanisms, but its predictive power has been severely limited by the lack of appropriate exchange-correlation functionals. Here, we show that there are many cases where the chemical bonding and van der Waals (vdW) interactions both play a key role in chemical reactions on surfaces. After briefly introducing some DFT methods and basic theory in chemical reactions, we first demonstrate that DFT can help to understand the mechanisms of “classic” reactions that mainly dominated by covalent bonding and vdW forces, as exemplified in electrocatalytic reduction of CO2 and the fabrication of 2D materials on metal substrates. We next show that DFT calculations can help to uncover the tautomerization reactions of molecules on metal surfaces, wherein the hydrogen bonding and vdW forces would largely affect the reaction process. More importantly, we show that in some cases, the vdW interactions can become the decisive effect that determines the adsorption configuration, energy hierarchy, and the potential-energy surface of chemical reactions, yielding distinct pathways and products. Additionally, we highlight the importance of more realistic conditions, such as surface defects, finite coverage, and temperature effects, in accurate modeling of chemical reactions. Finally, we summarize some challenges in modeling catalysis, which include many-body dispersive correction, strong correlation effect, and non-adiabatic approximations.

中文翻译：

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模拟表面上的化学反应：化学键和范德华相互作用的作用

摘要 表面上的化学反应在多相催化中起着核心作用，大多数反应涉及键的形成和/或断裂。目前，密度泛函理论（DFT）已成为反应机制计算研究的主力，但由于缺乏适当的交换相关泛函，其预测能力受到严重限制。在这里，我们表明在许多情况下，化学键和范德华 (vdW) 相互作用在表面的化学反应中都起着关键作用。在简要介绍了化学反应中的一些 DFT 方法和基本理论之后，我们首先证明了 DFT 有助于理解主要以共价键和 vdW 力为主的“经典”反应的机制，例如电催化还原 CO2 和在金属基材上制造二维材料。我们接下来表明 DFT 计算可以帮助揭示金属表面上分子的互变异构反应，其中氢键和 vdW 力将在很大程度上影响反应过程。更重要的是，我们表明，在某些情况下，vdW 相互作用可以成为决定化学反应的吸附构型、能量等级和势能表面的决定性作用，产生不同的途径和产物。此外，我们强调了更现实条件的重要性，例如表面缺陷、有限覆盖和温度效应，在化学反应的精确建模中。最后，我们总结了建模催化的一些挑战，