Smeets Egidius W F, Kroes Geert-Jan
Univeristeit Leiden, Leiden Institute of Chemistry, Einsteinweg 55, 2333 CC, Leiden, The Netherlands.
Phys Chem Chem Phys. 2021 Apr 7;23(13):7875-7901. doi: 10.1039/d0cp05173j. Epub 2020 Dec 8.
Specific reaction parameter density functionals (SRP-DFs) that can describe dissociative chemisorption molecular beam experiments of hydrogen (H) on cold transition metal surfaces with chemical accuracy have so far been shown to be only transferable among different facets of the same metal, but not among different metals. We design new SRP-DFs that include non-local vdW-DF2 correlation for the H + Cu(111) system, and evaluate their transferability to the highly activated H + Ag(111) and H + Au(111) systems and the non-activated H + Pt(111) system. We design our functionals for the H + Cu(111) system since it is the best studied system both theoretically and experimentally. Here we demonstrate that a SRP-DF fitted to reproduce molecular beam sticking experiments for H + Cu(111) with chemical accuracy can also describe such experiments for H + Pt(111) with chemical accuracy, and vice versa. Chemically accurate functionals have been obtained that perform very well with respect to reported van der Waals well geometries, and which improve the description of the metal over current generalized gradient approximation (GGA) based SRP-DFs. From a systematic comparison of our new SRP-DFs that include non-local correlation to previously developed SRP-DFs, for both activated and non-activated systems, we identify non-local correlation as a key ingredient in the construction of transferable SRP-DFs for H interacting with transition metals. Our results are in excellent agreement with experiment when accurately measured observables are available. It is however clear from our analysis that, except for the H + Cu(111) system, there is a need for more, more varied, and more accurately described experiments in order to further improve the design of SRP-DFs. Additionally, we confirm that, when including non-local correlation, the sticking of H on Cu(111) is still well described quasi-classically.
到目前为止，已证明能够以化学精度描述氢（H）在冷过渡金属表面的解离化学吸附分子束实验的特定反应参数密度泛函（SRP-DF）仅可在同一金属的不同晶面之间转移，而不能在不同金属之间转移。我们设计了新的SRP-DF，其中包括用于H + Cu(111)体系的非局域vdW-DF2相关，并评估它们对高活化的H + Ag(111)和H + Au(111)体系以及非活化的H + Pt(111)体系的可转移性。我们针对H + Cu(111)体系设计泛函，因为它是理论和实验研究得最为充分的体系。在此我们证明，一个以化学精度拟合以重现H + Cu(111)分子束吸附实验的SRP-DF，也能够以化学精度描述H + Pt(111)的此类实验，反之亦然。已获得化学精度的泛函，它们在已报道的范德华阱几何结构方面表现出色，并且相对于当前基于广义梯度近似（GGA）的SRP-DF改进了对金属的描述。通过对我们包含非局域相关的新SRP-DF与先前开发的SRP-DF在活化和非活化体系方面的系统比较，我们确定非局域相关是构建用于H与过渡金属相互作用的可转移SRP-DF的关键要素。当有精确测量的可观测量时，我们的结果与实验结果高度吻合。然而，从我们的分析中可以清楚地看出，除了H + Cu(111)体系外，需要更多、更多样化且描述更准确的实验，以便进一步改进SRP-DF的设计。此外，我们证实，当包含非局域相关时，H在Cu(111)上的吸附仍能很好地用准经典方法描述。
