Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces
Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces
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DOI：
10.1021/acs.jctc.6b01156
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发表时间：
2017-02-01
影响因子：
5.5
通讯作者：
Truhlar, Donald G.
中科院分区：
文献类型：
--
作者：
Duanmu, Kaining;Truhlar, Donald G.
自由基和分子在表面的吸附能的定量预测对于设计和理解非均相催化过程至关重要。Wellendorff等人最近的一篇论文收集了39个反应能的实验数据库，这些反应能涉及过渡金属表面的吸附能，可作为测试量子力学电子结构方法的基准，我们将实验数据与具有六个交换相关泛函的Kohn-Sham密度泛函计算进行了比较。在本文中，我们将数据重新整理为两类：开壳自由基吸附反应和闭壳分子吸附反应。我们用PBE重新计算了吸附能，并用Wellendorff等人的论文中没有研究的三个官能团M06-L、GAM和MN15-L计算了吸附能；然后将我们的结果与基准数据进行比较。通过与数据库的比较，我们发现9个官能团中，牛皮- vdw、GAM和RPBE在开壳自由基吸附反应中表现最好，MN15-L在闭壳分子吸附反应中表现最好，其次是牛皮- vdw和M06-L。
The quantitative prediction of adsorption energies of radicals and molecules on surfaces is essential for the design and understanding of heterogeneous catalytic processes. A recent paper by Wellendorff et al. collected an experimental database of 39 reaction energies involving adsorption energies on transition metal surfaces that can be used as benchmarks for testing quantum mechanical electronic structure methods, and we compared the experimental data to Kohn-Sham density functional calculations with six exchange-correlation functionals. In this paper, we rearranged the data into two categories: open-shell radical adsorption reactions and closed-shell molecular adsorption reactions. We recalculated the adsorption energies with PBE, and we also calculated them with three functionals, M06-L, GAM, and MN15-L, that were not studied in the Wellendorff et al. paper; then we compared our results to the benchmark data. Of the nine functionals that have been compared to the databases, we find that BEEF-vdW, GAM, and RPBE perform best for the open-shell radical adsorption reactions, and MN15-L performs best for the closed-shell molecular adsorption, followed by BEEF-vdW and M06-L.