Strong Vibrational Relaxation of NO Scattered from Au(111): Importance of the Adiabatic Potential Energy Surface

Yin, Rongrong; Zhang, Yaolong; Jiang, Bin

doi:10.1021/acs.jpclett.9b01806

Cited by 41 publications

(79 citation statements)

References 52 publications

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“…We also note that the MDEF(ODF) description slightly overestimates the elastic population for v i = 11 but underestimates it for v i = 16. The adiabatic results (previously discussed by some of us 40 ) capture a significant portion of multiquantum loss for v i = 11 and v i = 16, where the dominant vibrational scattering channels are 3 and 5 quanta loss respectively, though this is around half of what is predicted by experiment.…”

Section: Resultsmentioning

confidence: 64%

Determining the Effect of Hot Electron Dissipation on Molecular Scattering Experiments at Metal Surfaces

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Zhang

Yin

et al. 2020

JACS Au

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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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Section: Resultsmentioning

confidence: 64%

Determining the Effect of Hot Electron Dissipation on Molecular Scattering Experiments at Metal Surfaces

Box

Zhang

Yin

et al. 2020

JACS Au

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“…Indeed, previous studies on these systems have suggested that energy loss to surface phonons is much more dominant than that to EHPs using LDFA and/or neglecting the influence of surface motion on electronic friction. 9,71 It is interesting to see whether the tensorial electronic friction would lead to more significant nonadiabatic effects in these systems. It is also hopeful that this work can inspire future machine learning methods for describing other tensorial properties of molecules which possess a similar intertwined symmetry.…”

Section: Discussionmentioning

confidence: 99%

Symmetry-Adapted High Dimensional Neural Network Representation of Electronic Friction Tensor of Adsorbates on Metals

2019

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Nonadiabatic effects in chemical reaction at metal surfaces, due to excitation of electron-hole pairs, stand at the frontier of the studies of gas-surface reaction dynamics.However, the first principles description of electronic excitation remains challenging.In an efficient molecular dynamics with electronic friction (MDEF) method, the nonadiabatic couplings are effectively included in a so-called electronic friction tensor (EFT), which can be computed from first-order time-dependent perturbation theory (TDPT) in terms of density functional theory (DFT) orbitals. This second-rank tensor depends on adsorbate position and features a complicated transformation with regard to the intrinsic symmetry operations of the system. In this work, we develop a new symmetry-adapted neural network representation of EFT, based on our recently proposed embedded atom neural network (EANN) framework. Inspired by the derivation of the nonadiabatic coupling matrix, we represent the tensorial friction by the first and second derivatives of multiple outputs of NNs with respect to atomic Cartesian coordinates. This rigorously preserves the positive semidefiniteness, directional property, and correct symmetry-equivariance of EFT. Unlike previous methods, our new approach can readily include both molecular and surface degrees of freedom, regardless of the type of surface. Tests on the H2+Ag(111) system show that this approach yields an accurate, efficient, and continuous representation of EFT, making it possible to perform large scale TDPT-based MDEF simulations to study both adiabatic and nonadiabatic energy dissipation in a unified framework.

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“…This is at least partly due to the fact that the adiabatic PES used here also has no dissociation channel. Since then, a more realistic PES has been developed, one that is less attractive and allows for dissociative adsorption of NO on Au(111) 319,320 . Adiabatic calculations using this PES predict enhanced multiquantum vibrational relaxation, but still substantially less than seen in experiment.…”

Section: Dissipation and Inelastic Scatteringmentioning

confidence: 99%

Chemical dynamics from the gas‐phase to surfaces

2021

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The field of gas‐phase chemical dynamics has developed superb experimental methods to probe the detailed outcome of gas‐phase chemical reactions. These experiments inspired and benchmarked first principles dynamics simulations giving access to an atomic scale picture of the motions that underlie these reactions. This fruitful interplay of experiment and theory is the essence of a dynamical approach perfected on gas‐phase reactions, the culmination of which is a standard model of chemical reactivity involving classical trajectories or quantum wave packets moving on a Born–Oppenheimer potential energy surface. Extending the dynamical approach to chemical reactions at surfaces presents challenges of complexity not found in gas‐phase study as reactive processes often involve multiple steps, such as inelastic molecule‐surface scattering and dissipation, leading to adsorption and subsequent thermal desorption and or bond breaking and making. This paper reviews progress toward understanding the elementary processes involved in surface chemistry using the dynamical approach. Key points The fruitful interplay between chemistry and physics leads to an atomic scale view of reactions taking places at catalytically active surfaces. Improved observations of chemical reactions taking place in complex environments drive the development of new approaches to theoretical chemistry. Complex reaction networks from real catalysts are boiled down to their elementary steps and examined from first principles.

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Strong Vibrational Relaxation of NO Scattered from Au(111): Importance of the Adiabatic Potential Energy Surface

Cited by 41 publications

References 52 publications

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

Symmetry-Adapted High Dimensional Neural Network Representation of Electronic Friction Tensor of Adsorbates on Metals

Chemical dynamics from the gas‐phase to surfaces

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