Determining the Effect of Hot Electron Dissipation on Molecular Scattering Experiments at Metal Surfaces.
Determining the Effect of Hot Electron Dissipation on Molecular Scattering Experiments at Metal Surfaces.
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DOI：
10.1021/jacsau.0c00066
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发表时间：
2021-02-22
期刊：
影响因子：
8
通讯作者：
Maurer RJ
中科院分区：
文献类型：
--
作者：
Box CL;Zhang Y;Yin R;Jiang B;Maurer RJ
在金属表面的热化学和光化学中，由电子和原子在相当能量和时间尺度上的协调运动产生的非绝热效应无处不在。受激（热）电子可以通过贡献状态依赖的反应概率来测量影响分子-金属反应。NO在Au（111）上的振动态间散射是这方面研究最多的例子之一，为发展各种非绝热理论提供了一个试验场。这个系统经常被引用为电子摩擦理论失败的主要例子，电子摩擦理论是一个非常有效的模型，用于解释由于金属中产生热电子而对金属吸附分子产生的耗散力。然而，对于任何系统，与实验相比的确切失败和它们的理论来源都没有确定，因为动态特性受到许多复合模拟误差的影响，而非绝热处理的质量只是其中之一。我们使用电子结构理论的高维机器学习表示来最小化量子化学产生的错误。这使我们能够对非绝热分子动力学的性能进行全面的定量分析，以描述NO在Au（111）上的振动态间散射，并直接与绝热结果进行比较。我们发现电子摩擦理论准确地预测了弹性和单量子能量损失，但低估了多量子能量损失，高估了高振动激发下的分子捕获。我们的分析表明，在摩擦理论中可以潜在地弥补多量子能量损失，而对捕获的高估构成了电子摩擦理论的真正崩溃。解决这种对催化和表面化学动态过程的高估可能需要更复杂的理论
Nonadiabatic effects that arise from the concerted motion of electrons and atoms at comparable energy and time scales are omnipresent in thermal and light-driven chemistry at metal surfaces. Excited (hot) electrons can measurably affect molecule–metal reactions by contributing to state-dependent reaction probabilities. Vibrational state-to-state scattering of NO on Au(111) has been one of the most studied examples in this regard, providing a testing ground for developing various nonadiabatic theories. This system is often cited as the prime example for the failure of electronic friction theory, a very efficient model accounting for dissipative forces on metal-adsorbed molecules due to the creation of hot electrons in the metal. However, the exact failings compared to experiment and their origin from theory are not established for any system because dynamic properties are affected by many compounding simulation errors of which the quality of nonadiabatic treatment is just one. We use a high-dimensional machine learning representation of electronic structure theory to minimize errors that arise from quantum chemistry. This allows us to perform a comprehensive quantitative analysis of the performance of nonadiabatic molecular dynamics in describing vibrational state-to-state scattering of NO on Au(111) and compare directly to adiabatic results. We find that electronic friction theory accurately predicts elastic and single-quantum energy loss but underestimates multiquantum energy loss and overestimates molecular trapping at high vibrational excitation. Our analysis reveals that multiquantum energy loss can potentially be remedied within friction theory whereas the overestimation of trapping constitutes a genuine breakdown of electronic friction theory. Addressing this overestimation for dynamic processes in catalysis and surface chemistry will likely require more sophisticated theories
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影响因子：
3.7
作者：
Kresse, G;Furthmuller, J
通讯作者：
Furthmuller, J
影响因子：
56.9
作者：
Huang, YH;Rettner, CT;Wodtke, AM
通讯作者：
Wodtke, AM
DOI：
10.1073/pnas.1312200110
发表时间：
2013-10-29
影响因子：
11.1
作者：
Bartels, Nils;Golibrzuch, Kai;Schaefer, Tim
通讯作者：
Schaefer, Tim
影响因子：
1.9
作者：
Engelhart, Daniel P.;Wagner, Roman J. V.;Schafer, Tim
通讯作者：
Schafer, Tim
影响因子：
4.4
作者：
Dou, Wenjie;Subotnik, Joseph E.
通讯作者：
Subotnik, Joseph E.