Halldin Stenlid Joakim, Johansson Adam Johannes, Brinck Tore
Applied Physical Chemistry, Department of Chemistry, CBH, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden.
Swedish Nuclear Fuel and Waste Management Co (SKB), Evenemangsgatan 13, Box 3091, SE-169 03, Solna, Sweden.
Phys Chem Chem Phys. 2019 Aug 21;21(31):17001-17009. doi: 10.1039/c9cp03099a. Epub 2019 Jul 26.
Two local reactivity descriptors computed by Kohn-Sham density functional theory (DFT) are used to predict and rationalize interactions of nucleophilic molecules (exemplified by CO and HO) with transition metal (TM) and oxide surfaces. The descriptors are the electrostatic potential, V(r), and the local electron attachment energy, E(r), evaluated on surfaces defined by the 0.001 e Bohr isodensity contour. These descriptors have previously shown excellent abilities to predict regioselectivity and rank molecular as well as nanoparticle reactivities and interaction affinities. In this study, we generalize the descriptors to fit into the framework of periodic DFT computations. We also demonstrate their capabilities to predict local surface propensity for interaction with Lewis bases. It is shown that E(r) and V(r) can rationalize the interaction behavior of TM oxides and of fcc TM surfaces, including low-index, stepped and kinked surfaces spanning a wide range of interaction sites with varied coordination environments. Broad future applicability in surface science is envisaged for the descriptors, including heterogeneous catalysis and electrochemistry.
通过科恩-沈密度泛函理论（DFT）计算得到的两个局部反应性描述符，用于预测亲核分子（以CO和HO为例）与过渡金属（TM）及氧化物表面的相互作用，并对其进行合理的解释。这些描述符是静电势V(r)和局部电子附着能E(r)，它们是在由0.001 e玻尔等密度轮廓定义的表面上进行评估的。这些描述符此前已显示出卓越的能力，能够预测区域选择性、对分子以及纳米颗粒的反应性和相互作用亲和力进行排序。在本研究中，我们对这些描述符进行了推广，使其适用于周期性DFT计算的框架。我们还展示了它们预测与路易斯碱相互作用的局部表面倾向的能力。结果表明，E(r)和V(r)能够合理地解释TM氧化物和fcc TM表面的相互作用行为，包括具有各种配位环境、跨越广泛相互作用位点的低指数、阶梯状和扭结状表面。预计这些描述符在表面科学中具有广泛的未来适用性，包括多相催化和电化学。
