Ghassemi Elham Nour, Smeets Egidius W F, Somers Mark F, Kroes Geert-Jan, Groot Irene M N, Juurlink Ludo B F, Füchsel Gernot
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Institut für Chemie und Biochemie-Physikalische und Theoretische Chemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany.
J Phys Chem C Nanomater Interfaces. 2019 Feb 7;123(5):2973-2986. doi: 10.1021/acs.jpcc.8b11018. Epub 2019 Jan 4.
The accurate description of heterogeneously catalyzed reactions may require chemically accurate evaluation of barriers for reactions of molecules at the edges of metal nanoparticles. It was recently shown that a semiempirical density functional describing the interaction of a molecule dissociating on a flat metal surface (CHD + Pt(111)) is transferable to the same molecule reacting on a stepped surface of the same metal (Pt(211)). However, validation of the method for additional systems is desirable. To address the question whether the specific reaction parameter (SRP) functional that describes H + Pt(111) with chemical accuracy is also capable of accurately describing H + Pt(211), we have performed molecular beam simulations with the quasi-classical trajectory (QCT) method, using the SRP functional developed for H + Pt(111). Our calculations used the Born-Oppenheimer static surface model. The accuracy of the QCT method was assessed by comparison with quantum dynamics results for reaction of the ro-vibrational ground state of H. The theoretical results for sticking of H and D on Pt(211) are in quite good agreement with the experiment, but uncertainties remain because of a lack of accuracy of the QCT simulations at low incidence energies and possible inaccuracies in the reported experimental incidence energies at high energies. We also investigated the nonadiabatic effect of electron-hole pair excitation on the reactivity using the molecular dynamics with the electron friction (MDEF) method, employing the local density friction approximation (LDFA). Only small effects of electron-hole pair excitation on sticking are found.
对非均相催化反应的准确描述可能需要对金属纳米颗粒边缘分子反应的势垒进行化学精确评估。最近的研究表明，一种描述分子在平坦金属表面（CHD + Pt(111)）解离相互作用的半经验密度泛函可转移到同一分子在相同金属的阶梯表面（Pt(211)）上的反应。然而，需要对该方法在其他体系中的有效性进行验证。为了解决描述H + Pt(111)具有化学精度的特定反应参数（SRP）泛函是否也能够准确描述H + Pt(211)这一问题，我们使用为H + Pt(111)开发的SRP泛函，通过准经典轨迹（QCT）方法进行了分子束模拟。我们的计算使用了玻恩 - 奥本海默静态表面模型。通过与H的振转基态反应的量子动力学结果进行比较，评估了QCT方法的准确性。H和D在Pt(211)上吸附的理论结果与实验结果相当吻合，但由于低入射能量下QCT模拟的精度不足以及高能量下报道的实验入射能量可能存在的不准确，仍存在不确定性。我们还使用带有电子摩擦的分子动力学（MDEF）方法，采用局部密度摩擦近似（LDFA），研究了电子 - 空穴对激发对反应活性的非绝热效应。结果发现电子 - 空穴对激发对吸附的影响很小。
