Six-dimensional potential energy surfaces of the dissociative chemisorption of HCl on Ag(111) with three density functionals.
Six-dimensional potential energy surfaces of the dissociative chemisorption of HCl on Ag(111) with three density functionals.
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DOI：
10.1063/1.5036805
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发表时间：
2018-08
期刊：
影响因子：
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通讯作者：
Tianhui Liu;Bina Fu;Dong H. Zhang
中科院分区：
文献类型：
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作者：
Tianhui Liu;Bina Fu;Dong H. Zhang
我们首次构造了六维势能面(PESS)用于HCl在刚性Ag(111)表面的解离吸附。分别采用Perdew-Burke-Ernzerhof泛函、Perdew-Wang91泛函和修正的Perdew-Burke-Ernzerhof泛函，采用基于扩展密度泛函理论(DFT)的神经网络方法计算了三个全局PES。基于较小的拟合误差以及拟合后的PESS与直接DFT计算之间的良好一致性，得到的三个PESS都是精确拟合和光滑的。随时间变化的波包计算表明，PESS在拟合过程和DFT数据点数目方面都具有很好的收敛特性。给出并讨论了三种量子体系的比较结果以及三种体系的含时量子动力学结果。位平均近似对TITLE反应的有效性是成立的，其中25位平均四维解离几率可以准确地再现当前三个PESS上的六维解离几率。我们期望目前的理论研究能够促进这种气相-表面反应的实验工作。
We first constructed six-dimensional potential energy surfaces (PESs) for the dissociative chemisorption of HCl on rigid Ag(111). Three global PESs were calculated using the neural network method based on extensive density functional theory (DFT) calculations with Perdew-Burke-Ernzerhof, Perdew-Wang91, and revised Perdew-Burke-Ernzerhof functionals, respectively. The resulting three PESs are all accurately fitted and smooth, based on the small fitting errors and good agreements between the fitted PESs and the direct DFT calculations. Time-dependent wave packet calculations show that the PESs are very well converged with respect to the fitting process, as well as the number of DFT data points. Comparisons of three PESs and time-dependent quantum dynamics results on the three PESs were given and discussed. The validity of site-averaging approximation holds for the title reaction, where the 25 site-averaged four-dimensional dissociation probability can accurately reproduce the six-dimensional dissociation probability on the current three PESs. We expect that the current theoretical investigations can stimulate the experimental work for this gas-surface reaction.