Nuclear quantum effect for hydrogen adsorption on Pt(111)
Nuclear quantum effect for hydrogen adsorption on Pt(111)
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DOI：
10.1103/physrevb.101.165414
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发表时间：
2020-04
影响因子：
3.7
通讯作者：
Lei Yan;Yoshiyuki Yamamoto;M. Shiga;O. Sugino
中科院分区：
文献类型：
--
作者：
Lei Yan;Yoshiyuki Yamamoto;M. Shiga;O. Sugino
我们的从头算路径积分和环聚合物分子动力学模拟表明，在高覆盖度的电化学条件下，氢原子在Pt（111）体系中的核量子效应和多体相互作用是重要的。在整个单层覆盖下，由于氢原子的强排斥作用和吸附位的近简并性质，氢原子在顶位或面心立方位都是紧密堆积的。而在2/3单层膜中，由于跳跃作用，它们通过桥位离域到fcc和hcp位上。因此，量子多体效应在确定覆盖依赖性方面至关重要，并为调和该系统的长期争议提供了线索。
Nuclear quantum effect and many-body interaction importantly interplay in the hydrogen on the Pt(111) system under the high coverage conditions of electrochemical interest, as revealed by our ab initio path integral and ring polymer molecular dynamics simulations done at room temperature. At the full monolayer coverage, hydrogen atoms are close-packed either at the atop sites or the fcc sites owing to their strong repulsion and the nearly degenerate nature of the adsorption sites. While at the 2/3 monolayer, they are delocalized over the fcc and hcp sites via the bridge sites because of the hopping. The quantum many-body effect is thus crucially important in determining the coverage dependence and provides a clue for reconciling the long-standing controversy on this system.