Abstract:Conversion of energy at the gas-solid interface lies at the heart of many industrial applications such as heterogeneous catalysis. Dissipation of parts of this energy into the substrate bulk drives the thermalization of surface species, but also constitutes a potentially unwanted loss channel. At present, little is known about the underlying microscopic dissipation mechanisms and their (relative) efficiency. At metal surfaces, prominent such mechanisms are the generation of substrate phonons and the electronic… Show more
“…Through surface correlation measurements, HeSE offers a unique way to measure rates of energy transfer, and thus the strength of energetic coupling. 113,122,123 The method has been used to measure atomic scale frictional coupling constants, 124 explain the absolute rate of motion in complex systems, 125 and to test quantum rate theories. 119 3.6.4 Ultra low energy vibrational properties.…”
Helium Atom Scattering (HAS) and Helium Spin Echo scattering (HeSE), together Helium Scattering, are well established, but non-commercial surface science techniques. They are characterised by the beam inertness and very...
“…Through surface correlation measurements, HeSE offers a unique way to measure rates of energy transfer, and thus the strength of energetic coupling. 113,122,123 The method has been used to measure atomic scale frictional coupling constants, 124 explain the absolute rate of motion in complex systems, 125 and to test quantum rate theories. 119 3.6.4 Ultra low energy vibrational properties.…”
Helium Atom Scattering (HAS) and Helium Spin Echo scattering (HeSE), together Helium Scattering, are well established, but non-commercial surface science techniques. They are characterised by the beam inertness and very...
“… 2 As a result, the gaseous species in the vicinity of a metal surface can easily dissipate their energy not only by exciting lattice vibrations but also through electronâhole pair excitations (EHPs). 3 Indeed, there has been growing experimental evidence of such nonadiabatic effects in surface chemistry 4 from quantum-state-resolved molecular beam scattering experiments, 5 chemicurrent measurements, 6 , 7 and ultrafast spectroscopy, 8 providing valuable benchmark data for testing first-principles theories of nonadiabatic gas-surface interactions. 9 However, a predictive quantitation of how nonadiabatic effects contribute to measurable dynamic properties remains elusive.…”
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 moleculeâmetal 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
“…Energy exchange between adsorbate and substrate degrees of freedom (DOFs) has a potentially significant impact on chemical reaction dynamics at solid surfaces 1. At metal surfaces, in particular, energy carried by the adsorbate could dissipate to either surface phonons or electrons 2. Due to the continuous distribution of metallic electronic states across the Fermi level, the excitation of electronâhole pairs (EHPs) can be induced by the interaction between the adsorbate and metal atoms with the electrons in the metal surface 3,4.…”
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citationsâcitations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.