When is electronic friction reliable for dynamics at a molecule–metal interface?

Coffman, Alec J.; Subotnik, Joseph E.

doi:10.1039/c7cp08249e

Cited by 14 publications

(14 citation statements)

References 48 publications

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“…When the Massey parameter approaches 1, any method that does not incorporate several possible paths will be unable to properly model the dynamics. This result is consistent with that of Coffman and Subotnik 25 , where it has been concluded that a friction approach seems to fail in the case where there are nonequivalent pathways. Such behavior can be explained by the breakdown of the underlining EH theory as opposed to an intrinsic failure of the friction approach.…”

Section: Discussionsupporting

confidence: 92%

On the breakdown of the Ehrenfest method for molecular dynamics on surfaces

Loaiza

Izmaylov

2018

The Journal of Chemical Physics

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Due to a continuum of electronic states present in periodic systems, the description of molecular dynamics on surfaces poses a serious computational challenge. One of the most used families of approaches in these settings are friction theories, which are based on the Ehrenfest (EH) approach. Yet, a mean-field treatment of electronic degrees of freedom in the EH method makes this approach inaccurate in some cases. Our aim is to clarify when EH breaks down for molecular dynamics on surfaces. Answering this question provides limits of applicability for more approximate friction theories derived from EH. We assess the EH method on one-dimensional, numerically exactly solvable models with a large but finite number of electronic states. Using the Landau-Zener formula and the Massey parameter, an expression that determines when EH breaks down is deduced. arXiv:1809.03829v1 [physics.chem-ph]

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Section: Discussionsupporting

confidence: 92%

On the breakdown of the Ehrenfest method for molecular dynamics on surfaces

Loaiza

Izmaylov

2018

The Journal of Chemical Physics

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“…In other words, how do we know when the weak-coupling limit is satisfied and when the MDEF method is reliable for a particular system? While this question was partially addressed by Dou and Subotnik for simple model systems, 29 here we provide quantitative insights for state-to-state scattering of NO from Au(111), which has been considered a representative strong-coupling showcase for the breakdown of electronic friction theory. 30 , 31 …”

Section: Introductionmentioning

confidence: 88%

“…In practice, the MDEF method is always further approximated by imposing the Markov approximation of instantaneous response in the constant coupling limit, where some pragmatic assumptions are made in how the friction tensor is calculated from DFT in that limit . Examples of approximations include the local density friction approximation (LDFA), which allows for an efficient calculation of scalar isotropic friction from the electron density of the metal ,− and the more realistic orbital-dependent friction (ODF), , which is calculated from Kohn–Sham DFT via time-dependent perturbation theory to provide a better description of the mode-selective nature of nonadiabatic molecule-metal energy transfer. − …”

Section: Introductionmentioning

confidence: 99%

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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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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“…The electronic friction tensor lies at the core of the definition of the friction force in MDEF and can be understood as a first order correction to the Born-Oppenheimer approximation in the presence of a manifold of fast relaxing electronic states 16 . As a consequence, MDEF is expected to break down when strong non-adiabatic effects are present 1,17 and in cases where charge a) Electronic mail: yairlitman@gmail.com b) Electronic mail: mariana.rossi@mpsd.mpg.de transfer mechanisms are dominant 11 . Despite these shortcomings, MDEF has proven to be a useful approach for several realistic systems and conditions, in which high-level simulations can explain well-controlled experiments 6,9,[18][19][20][21] .…”

Section: Introductionmentioning

confidence: 99%

Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory

Litman,

Pós,

Box

et al. 2022

Preprint

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Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modelling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to firstprinciples calculations of reaction rates in high-dimensional realistic systems. In more detail, we develop a method that we coin mean-field ring polymer instanton (MF-RPI), starting from the ring-polymer instanton formalism applied to a system-bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor, and then combine this method with the ab initio electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between MF-RPI and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.

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When is electronic friction reliable for dynamics at a molecule–metal interface?

Cited by 14 publications

References 48 publications

On the breakdown of the Ehrenfest method for molecular dynamics on surfaces

On the breakdown of the Ehrenfest method for molecular dynamics on surfaces

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

Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory I: Theory

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