论文标题
确定热电子耗散对金属表面上分子散射实验的影响
Determining the effect of hot electron dissipation on molecular scattering experiments at metal surfaces
论文作者
论文摘要
在金属表面的热和轻度驱动化学中,电子和原子在可比的能量和时间尺度上的一致运动产生的非绝热效应。激发(热)电子可以通过有助于状态依赖性反应概率来衡量地影响分子 - 金属反应。 NO在AU(111)上的振动状态到州散射一直是这方面研究最多的例子之一,为开发各种非绝热理论提供了测试场。该系统通常被认为是电子摩擦理论失败的主要示例,这是一个非常有效的模型,该模型是由于金属中的热电子创建了金属吸附分子上的耗散力。但是,与实验相比,确切的失败并未针对任何系统建立,因为动态属性受到许多复合模拟误差的影响,而非绝热治疗的质量只是一种。我们使用电子结构理论的高维机学习表示,以最大程度地减少量子化学产生的误差。这使我们能够对非脱绝热分子动力学的性能进行全面的定量分析,以描述AU上NO的振动状态到状态散射(111)(111),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,并高估了在高振动激发下的分子捕获。我们的分析表明,在摩擦理论中可能会补救多量子能量损失,而高估陷阱构成了电子摩擦理论的真正分解。解决这种高估催化和表面化学中动态过程的高估将需要更复杂的理论。
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 multi-quantum energy loss and overestimates molecular trapping at high vibrational excitation. Our analysis reveals that multi-quantum 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 require more sophisticated theories.