A remarkable heavy atom isotope effect in the dissociative chemisorption of nitrogen on Ru(001)

Romm, L.; Citri, O.; Kosloff, Ronnie; Asscher, Micha

doi:10.1063/1.481476

Cited by 27 publications

(43 citation statements)

References 21 publications

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“…As it was shown in Refs. 30 and 31, these theoretical results reproduce the surprisingly low dissociation probabilities [27,[50][51][52] found in the experiments. The results can be understood based on the very special characteristics of the N 2 /Ru(0001) PES: [28,30,31,51] The minimum barrier is very high, around 2.3 eV, and the PES displays high anisotropy and corrugation, i.e., small changes in the orientation and/or the position of the molecule gives rise to large changes in the potential energy (see Fig.…”

Section: A 6d Dynamics and The Vibrational Efficacysupporting

confidence: 71%

“…This has now been reported for a number of systems, CH 4 /Ni(111) [23,24], CH 4 /Ni(100) [25], CH 4 /Ru(0001) [26] and even for the "simple" N 2 /Ru(0001) [27,28] case. Several hypotheses have been proposed in order to explain the "surprising" results Θ vib (R) > 1: It has been suggested that if the asymptotic reactivity (i.e., the saturation value of the dissociation probability) increases for vibrationally excited molecules, then Eq.…”

Section: Introductionmentioning

confidence: 52%

“…1, we find Θ vib (R) ≈ 1.6 for R in the range 0.0005-0.1. [31] This value is smaller than the Θ vib (R) ≈ 2.5 that can be estimated from experiments, [27] but both results are significantly larger than 1. There are a number of possible explanations for the rather large difference in efficacy found by theory and experiments: On the theoretical side it is possible that the PES calculated by DFT is not close enough to the actual PES governing the dynamics of the system.…”

Section: A 6d Dynamics and The Vibrational Efficacymentioning

confidence: 62%

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A note on the vibrational efficacy in molecule-surface reactions

Dı́az¹,

Olsen²

2009

The Journal of Chemical Physics

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The effectiveness of vibrational energy in promoting dissociation of molecules colliding with surfaces can be measured through the so-called vibrational efficacy. It is by many thought to be a pure "energetic" measure and therefore believed to be limited from below by zero (in the case that there is no increase in dissociation probability upon vibrational excitation) and from above by one (in the case that all of the vibrational excitation energy is used to promote reaction).However, the quantity vibrational efficacy is clearly linked to the detailed dynamics of the system, and straightforward considerations lead to the conclusion that it is not limited either from below or above. Here we discuss these considerations together with a quasi-classical dynamics study of a molecule-surface system, N 2 /Ru(0001), for which a vibrational efficacy bigger than one has been found both experimentally and theoretically. We show that an analysis of the vibrational efficacy only in terms of energy transfer from vibration to translation can be too simple to describe the behavior of systems for which the potential energy surfaces present (high) reaction barriers, potential corrugation and anisotropy, and curved reaction paths.

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Section: A 6d Dynamics and The Vibrational Efficacysupporting

confidence: 71%

Section: Introductionmentioning

confidence: 52%

Section: A 6d Dynamics and The Vibrational Efficacymentioning

confidence: 62%

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A note on the vibrational efficacy in molecule-surface reactions

Dı́az¹,

Olsen²

2009

The Journal of Chemical Physics

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“…At an energy of 0.1 eV below the threshold energy ͑1.15 eV͒, the reaction probability has already a value below 10 −5 . This result is in sharp contrast to the results of previous model calculations of the dissociation probability for N 2 on various metal surfaces, [66][67][68][69][70][71][72] where significant reaction probabilities ͑Ϸ10 −5 ͒ have been found for more than 0.3 eV below the barrier energy. Note that N͑E͒ is an upper bound to the initial state-selected reaction probabilities since it is the sum of all reaction probabilities.…”

Section: Resultscontrasting

confidence: 56%

“…[66][67][68][69][70][71][72] These calculations show a significant tunneling effect on the reaction probability. As discussed by Haase et al, 67 the results suggest that at room temperature the reaction is completely dominated by a tunneling mechanism, 67 which is quite surprising for a heavy-atom system.…”

Section: Introductionmentioning

confidence: 96%

The reaction rate for dissociative adsorption of N2 on stepped Ru(0001): Six-dimensional quantum calculations

Harrevelt

Honkala

Nørskov

et al. 2005

The Journal of Chemical Physics

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The reaction rate for dissociative adsorption of N 2 on stepped Ru"0001…: Six-dimensional quantum calculations Quantum-mechanical calculations of the reaction rate for dissociative adsorption of N 2 on stepped Ru͑0001͒ are presented. Converged six-dimensional quantum calculations for this heavy-atom reaction have been performed using the multiconfiguration time-dependent Hartree method. A potential-energy surface for the transition-state region is constructed from density-functional theory calculations using Shepard interpolation. The quantum results are in very good agreement with the results of the harmonic transition-state theory. In contrast to the findings of previous model calculations on similar systems, the tunneling effect is found to be small.

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Isotope effect suggests site‐specific nonadiabaticity on Ge(111)c(2×8)

Krüger,

Wang,

Zhu

et al. 2023

Natural Sciences

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Energy transferred in atom‐surface collisions typically depends strongly on projectile mass, an effect that can be experimentally detected by isotopic substitution. In this work, we present measurements of inelastic H and D atom scattering from a semiconducting Ge(111)c(2×8) surface exhibiting two scattering channels. The first channel shows the expected isotope effect and is quantitatively reproduced by electronically adiabatic molecular dynamics simulations. The second channel involves electronic excitations of the solid and, surprisingly, exhibits almost no isotope effect. We attribute these observations to scattering dynamics, wherein the likelihood of electronic excitation varies with the impact site engaged in the interaction.Key Points Previous work revealed that H atoms with sufficient translational energy can excite electrons over the band gap of a semiconductor in a surface collision. We studied the isotope effect of the energy transfer by H/D substitution and performed band structure calculations to elucidate the underlying excitation mechanism. Our results suggest a site‐specific mechanism that requires the atom to hit a specific surface site to excite an electron‐hole pair.

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A remarkable heavy atom isotope effect in the dissociative chemisorption of nitrogen on Ru(001)

Cited by 27 publications

References 21 publications

A note on the vibrational efficacy in molecule-surface reactions

A note on the vibrational efficacy in molecule-surface reactions

The reaction rate for dissociative adsorption of N2 on stepped Ru(0001): Six-dimensional quantum calculations

Isotope effect suggests site‐specific nonadiabaticity on Ge(111)c(2×8)

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