Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces

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• 作者：Kaining DuanmuDonald G. Truhlar
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2017
• 出版时间：February 14, 2017
• 年：2017
• 卷：13
• 期：2
• 页码：835-842
• 全文大小：256K
• ISSN：1549-9626

文摘

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.