Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An <i>ab initio</i> molecular dynamics study

Kolb, Brian; Guo, Hua

doi:10.1063/1.4956453

Cited by 36 publications

(54 citation statements)

References 29 publications

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“…From Ref. 104 , which also used the RPBE functional, a change of 0.07 can be extracted at ! F¬±Å² = 2.5 eV (the energy transferred to the surface was about 1100 meV).…”

Section: Aimd Resultsmentioning

confidence: 99%

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Enigmatic HCl + Au(111) Reaction: A Puzzle for Theory and Experiment

Füchsel

Cueto²,

Dı́az³

et al. 2016

J. Phys. Chem. C

134

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an accurate potential energy surface incorporating the six adsorbate degrees of freedom of HCl on Au(111) by using the neural network approach. In our molecular dynamics simulations, we model the experimental beam conditions to study the influence of the rovibrational state population distribution of HCl in the molecular beam on reaction. Likewise, molecular dynamics with electronic friction calculations based on the parameterfree local density friction approximation in the independent atom approximation (LDFA-IAA) are performed to get first insights into how electron hole pair excitation might affect the reactivity of HCl. Although satisfying agreement with the experiment could not yet be achieved by our simulations, we find that i) RPBE yields larger reaction barriers than PBE and lower computed reaction probabilities, improving the agreement with experiment, ii) the reactivity strongly depends on the rovibrational state population, iii) surface atom motion and electronically non-adiabatic effects modeled with the efficient to use but approximate LDFA influence the reaction only modestly, and iv) a moderate amount of charge is transferred from the surface to the dissociating molecule at the transition state. We suggest that the reported experimental reaction probabilities could be too low by a factor of about 2-3, due to potential problems with calibrating coverage of Au by Cl using an ill-defined external standard in the form of Auger peak ratios. However, taking this factor into account would not yet resolve the discrepancy between the theoretical reaction probabilities presented here and the experimental sticking probabilities.

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“…From Ref. 104 , which also used the RPBE functional, a change of 0.07 can be extracted at ! F¬±Å² = 2.5 eV (the energy transferred to the surface was about 1100 meV).…”

Section: Aimd Resultsmentioning

confidence: 99%

“…Reaction probabilities presented for DCl in Ref. 104 and vibrational motion of DCl in the gas phase. As will be shown below, however, the computed reaction probability critically depends on the initial conditions.…”

Section: Aimd Resultsmentioning

confidence: 99%

Enigmatic HCl + Au(111) Reaction: A Puzzle for Theory and Experiment

Füchsel

Cueto²,

Dı́az³

et al. 2016

J. Phys. Chem. C

134

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show abstract

“…The AIMD approach has very recently been used successfully in studying HCl scattering and dissociation on Au(111). 51,52 In addition to the AIMD studies, we have also carried out AIMD with electronic friction (AIMDEF) 47,53,54 calculations in which the possible involvement of EHPs in the energy dissipation of hot H atoms is explored with the LDFA approach. 48 The AIMDEF approach eliminates the uncertainties in the previous empirical treatment of the EHP effects.…”

Section: Introductionmentioning

confidence: 99%

Ab initio molecular dynamics study of the Eley-Rideal reaction of H + Cl–Au(111) → HCl + Au(111): Impact of energy dissipation to surface phonons and electron-hole pairs

Zhou

Alducin

et al. 2018

The Journal of Chemical Physics

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The reaction between an impinging H atom and a Cl atom adsorbed on Au(111), which is a prototype for the Eley-Rideal mechanism, is investigated using ab initio molecular dynamics at different incidence angles. The reaction yielding gaseous HCl with large internal excitation proceeds via both direct and hot-atom mechanisms. Significant energy exchange with both surface phonons and electron-hole pairs has been observed. However, their impact on the reactivity and final state distributions was found to be limited, thanks to the large exothermicity and small barrier of the reaction.

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“…Attempts to reproduce such sticking data from theory has shown that dissipation from phonons can require in some cases an explicit treatment of substrate motion, while satisfactory agreement is often already achieved on the level of effective energy sink models, or even a complete neglect of energy exchange with the lattice. While some prediction of the phononic relevance can be made based on the adsorbate-substrate mass mismatch, this does not always appear to be accurate [78,86,92]. This uncertainty adds yet another facet of complexity when considering also the contributing role of the non-adiabatic dissipation channel, whose relevance remains to date similarly obscure and inconclusive.…”

Section: Discussionmentioning

confidence: 99%

“…A prototypical such example is the dissociation of HCl on Au(1 1 1) for which energy dissipation is believed to play a key role [91]. While (independently performed) AIMD simulations [86,92] have consistently overestimated the experimental probabilities [91], the corresponding reaction dynamics of this system remain an enigma and have become quite a controversy in the field [86].…”

Section: Explicitly Resolving Surface Motionmentioning

confidence: 99%

Energy dissipation at metal surfaces

Rittmeyer

Bukas

Reuter

2017

Advances in Physics: X

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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 electronically non-adiabatic excitation of electron-hole pairs. In recent years, dedicated surface science experiments at defined single-crystal surfaces and predictive-quality firstprinciples simulations have increasingly been used to analyze these dissipation mechanisms in prototypical surface dynamical processes such as gas-phase scattering and adsorption, diffusion, vibration, and surface reactions. In this topical review we provide an overview of modeling approaches to incorporate dissipation into corresponding dynamical simulations starting from coarsegrained effective theories to increasingly sophisticated methods. We illustrate these at the level of individual elementary processes through applications found in the literature, while specifically highlighting the persisting difficulty of gauging their performance based on experimentally accessible observables.

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Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An ab initio molecular dynamics study

Cited by 36 publications

References 29 publications

Enigmatic HCl + Au(111) Reaction: A Puzzle for Theory and Experiment

Enigmatic HCl + Au(111) Reaction: A Puzzle for Theory and Experiment

Ab initio molecular dynamics study of the Eley-Rideal reaction of H + Cl–Au(111) → HCl + Au(111): Impact of energy dissipation to surface phonons and electron-hole pairs

Energy dissipation at metal surfaces

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