Closing the Gap Between Experiment and Theory: Reactive Scattering of HCl from Au(111)
Closing the Gap Between Experiment and Theory: Reactive Scattering of HCl from Au(111)
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DOI：
10.1021/acs.jpcc.0c03756
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发表时间：
2020-07-23
影响因子：
3.7
通讯作者：
Kroes, Geert-Jan
中科院分区：
文献类型：
--
作者：
Gerrits, Nick;Geweke, Jan;Kroes, Geert-Jan
分子在金属表面反应的准确模拟有助于改进多相催化剂，但对于一些反应来说，这仍然是遥不可及的。例如，尽管做了许多努力，但HCl与Au(111)反应的理论和实验之间仍然存在很大的分歧。本文用MGGA密度泛函(MS-RPBEI)和高维神经网络势研究了HCl在Au(111)面上的解离化学吸附。此外，对以前的实验粘连概率进行了重新检验。实验和理论之间的一致性得到了很大的改善，尽管理论仍然高估了最高入射能量下实验粘着几率的2-7倍。计算的振动跃迁几率和测量的振动跃迁几率也得到了改进的一致。一些动力学效应，如角转向和从分子到表面的能量转移，被发现起着重要的作用。
Accurate simulation of molecules reacting on metal surfaces, which can help in improving heterogeneous catalysts, remains out of reach for several reactions. For example, a large disagreement between theory and experiment for HCl reacting on Au(111) still remains, despite many efforts. In this work, the dissociative chemisorption of HCl on Au(111) is investigated with a recently developed MGGA density functional (MS-RPBEI) and a high-dimensional neural network potential. Additionally, previous experimental sticking probabilities are re-examined. A considerably improved agreement between experiment and theory is obtained, although theory still overestimates experimental sticking probabilities by a factor of 2-7 at the highest incidence energy. Computed and measured vibrational transition probabilities are also in improved agreement. Several dynamical effects such as angular steering and energy transfer from the molecule to the surface are found to play an important role.