Krupka Katarzyna M, Krzemińska Agnieszka, de Lara-Castells María Pilar
Institute of Fundamental Physics (AbinitSim Unit ABINITFOT Group), Consejo Superior de Investigaciones Científicas (CSIC) Madrid Spain
Institute of Physics, Lodz University of Technology ul. Wolczanska 219 90-924 Lodz Poland.
RSC Adv. 2024 Oct 2;14(43):31348-31359. doi: 10.1039/d4ra05401f. eCollection 2024 Oct 1.
Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up fascinating possibilities in designing new heterogeneous (photo)catalysts as well as functional interfaces between AMCs and biologically relevant molecules. Understanding the nature of AMC-support interactions at molecular-level is essential for optimizing (photo)catalysts performance and designing novel ones with improved properties. Møller-Plesset second-order perturbation theory (MP2) is one of the most cost-efficient single-reference post-Hartree-Fock wave-function-based theories that can be applied to AMC-support interactions considering adequate molecular models of the support, and thus complementing state-of-the-art dispersion-corrected density functional theory. However, the resulting AMC-support interaction is typically overestimated with the MP2 method and must be corrected. The coupled MP2 (MP2C) scheme replacing the uncoupled Hartree-Fock dispersion energy by a coupled dispersion contribution, has been proven to describe accurately van-der-Waals (vdW)-dominated interactions between closed-shell AMCs and carbon-based supports. In this work, the accuracy of a MP2C-based scheme is evaluated in modelling open-shell AMC-cluster interactions that imply charge transfer or other strong attractive energy contributions beyond vdW forces. For this purpose, we consider the interaction of Cu with molecular models of graphene of increasing size (benzene and coronene). In this way, it is shown that subchemical precision (within 0.1 kcal mol) is achieved with the modified MP2C scheme, using the explicitly correlated coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)-F12] as a benchmark method. It is also revealed that the energy difference between uncoupled and coupled dispersion terms closely follows benchmark values of the repulsive intramonomer correlation contribution. The proposed open-shell MP2C-based approach is expected to be of general applicability to open-shell atomic or molecular species interacting with coronene for regions of the potential landscape where single-reference electronic structure descriptions suffice.
目前在亚纳米尺度合成和表征原子精确的单分散金属簇（AMC）方面取得的进展，为设计新型多相（光）催化剂以及AMC与生物相关分子之间的功能界面开辟了迷人的可能性。在分子水平上理解AMC与载体相互作用的本质，对于优化（光）催化剂性能和设计具有改进性能的新型催化剂至关重要。莫勒-普莱塞二阶微扰理论（MP2）是最具成本效益的基于单参考后哈特里-福克波函数的理论之一，考虑到载体的适当分子模型，它可应用于AMC与载体的相互作用，从而补充了最先进的色散校正密度泛函理论。然而，用MP2方法得到的AMC与载体的相互作用通常被高估，必须进行校正。通过用耦合色散贡献取代非耦合哈特里-福克色散能的耦合MP2（MP2C）方案，已被证明能准确描述闭壳AMC与碳基载体之间以范德华（vdW）为主导的相互作用。在这项工作中，评估了基于MP2C的方案在模拟开壳AMC簇相互作用时的准确性，这种相互作用意味着电荷转移或除vdW力之外的其他强吸引能贡献。为此，我们考虑了铜与尺寸不断增大的石墨烯分子模型（苯和并五苯）的相互作用。结果表明，使用明确相关的耦合簇理论（含单、双和微扰三重激发）[CCSD(T)-F12]作为基准方法，经修正的MP2C方案实现了亚化学精度（在0.1 kcal/mol以内）。还揭示了非耦合和耦合色散项之间的能量差紧密遵循排斥性单体内相关贡献的基准值。所提出的基于开壳MP2C的方法预计在单参考电子结构描述足够的势能面区域，对与并五苯相互作用的开壳原子或分子物种具有普遍适用性。
