Jiang Bin, Guo Hua
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM 87131, USA.
Phys Chem Chem Phys. 2016 Aug 3;18(31):21817-24. doi: 10.1039/c6cp03707k.
In search for an accurate description of the dissociative chemisorption of water on the Ni(111) surface, we report a new nine-dimensional potential energy surface (PES) based on a large number of density functional theory points using the RPBE functional. Seven-dimensional quantum dynamical calculations have been carried out on the RPBE PES, followed by site averaging and lattice effect corrections, yielding sticking probabilities that are compared with both the previous theoretical results based on a PW91 PES and experiment. It is shown that the RPBE functional increases the reaction barrier, but has otherwise a minor impact on the PES topography. Better agreement with experimental results is obtained with the new PES, but the agreement is still not quantitative. Possible sources of the remaining discrepancies are discussed.
为了准确描述水在Ni(111)表面的解离化学吸附，我们报告了一种基于大量使用RPBE泛函的密度泛函理论点的新的九维势能面（PES）。在RPBE PES上进行了七维量子动力学计算，随后进行了位点平均和晶格效应校正，得到了 sticking概率，并与基于PW91 PES的先前理论结果和实验结果进行了比较。结果表明，RPBE泛函增加了反应势垒，但对PES形貌的影响较小。新的PES与实验结果取得了更好的一致性，但仍未达到定量水平。讨论了剩余差异的可能来源。
