Journal
JACS AU
Volume 1, Issue 2, Pages 164-173Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacsau.0c00066
Keywords
Nonadiabatic dynamics; gas surface scattering; metal surface; energy dissipation; electronic friction
Categories
Funding
- EPSRC
- UKRI Future Leaders Fellowship program [MR/S016023/1]
- National Key R&D Program of China [2017YFA0303500]
- National Natural Science Foundation of China [21722306, 91645202, 22073089]
- Anhui Initiative in Quantum Information Technologies [AHY090200]
- EPSRC [EP/R029431/1]
- UKRI [MR/S016023/1] Funding Source: UKRI
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The study examines nonadiabatic effects in thermal and light-driven chemistry on metal surfaces, particularly focusing on the scattering of NO on Au(111). The results indicate that electronic friction theory accurately predicts some aspects of the reaction, but underestimates certain energy loss and overestimates molecular trapping. More sophisticated theories may be required to address these discrepancies in dynamic processes in catalysis and surface chemistry.
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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