Publisher’s Note: Competition between Electron and Phonon Excitations in the Scattering of Nitrogen Atoms and Molecules off Tungsten and Silver Metal Surfaces [Phys. Rev. Lett.<b>108</b>, 096101 (2012)]

Martin-Gondre, L.; Alducin, M.; Bocan, G. A.; Muiño, R. Dı́ez; Juaristi, J. I.

doi:10.1103/physrevlett.108.139901

Cited by 24 publications

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“…22,29,30 A similar conclusion has been recently reached for the scattering of N 2 from W(110) and N from Ag(111). 24 In the particular case of H 2 interacting with copper, adiabatic calculations have been shown to give good results in comparison with experiments for H 2 /Cu(100), 31,32 H 2 /Cu(110) (Ref. 33), and H 2 /Cu(111).…”

Section: Introductionmentioning

confidence: 99%

“…15 Motivated by this controversy, an important number of theoretical methods that include electronic excitations have been recently developed. [16][17][18][19][20][21][22][23][24] In some cases, non-adiabatic dynamics based on low-dimensional calculations has resulted in overestimation of the effects associated with e-h pair excitations. For example, for N 2 /Ru(0001) it was claimed, 16 based on low-dimensional non-adiabatic calculations, that the huge discrepancy between low-dimensional adiabatic calculations and experiment was mostly due to e-h pair excitations, whereas a subsequent adiabatic high-dimensional dynamics study 25,26 showed that most of the discrepancy vanishes when the six degrees of freedom of the molecule are taken into account in the dynamics.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

Muzas

Juaristi

Alducin

et al. 2012

The Journal of Chemical Physics

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We have studied survival and rotational excitation probabilities of H 2 (v i = 1, J i = 1) and D 2 (v i = 1, J i = 2) upon scattering from Cu(111) using six-dimensional (6D) adiabatic (quantum and quasi-classical) and non-adiabatic (quasi-classical) dynamics. Non-adiabatic dynamics, based on a friction model, has been used to analyze the role of electron-hole pair excitations. Comparison between adiabatic and non-adiabatic calculations reveals a smaller influence of non-adiabatic effects on the energy dependence of the vibrational deexcitation mechanism than previously suggested by low-dimensional dynamics calculations. Specifically, we show that 6D adiabatic dynamics can account for the increase of vibrational deexcitation as a function of the incidence energy, as well as for the isotope effect observed experimentally in the energy dependence for H 2 (D 2 )/Cu(100). Furthermore, a detailed analysis, based on classical trajectories, reveals that in trajectories leading to vibrational deexcitation, the minimum classical turning point is close to the top site, reflecting the multidimensionally of this mechanism. On this site, the reaction path curvature favors vibrational inelastic scattering. Finally, we show that the probability for a molecule to get close to the top site is higher for H 2 than for D 2 , which explains the isotope effect found experimentally.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

Muzas

Juaristi

Alducin

et al. 2012

The Journal of Chemical Physics

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“…Tungsten surfaces, among others, have received much attention [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21], with particular focus on the large crystallographic anisotropy that this metal exhibits with respect to nitrogen adsorption. For instance, the thermal reactivity of W(100) is about two orders of magnitude larger than the W(110) reactivity [2].…”

Section: Introductionmentioning

confidence: 99%

N2 dissociation on W(110): An ab initio molecular dynamics study on the effect of phonons

Nattino

Costanzo

Kroes

2015

The Journal of Chemical Physics

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Accurately modeling the chemisorption dynamics of N 2 on metal surfaces is of both practical and fundamental interest. The factors that may have hampered this achievement so far are the lack of an accurate density functional and the use of approximate methods to deal with surface phonons and non-adiabatic effects. In the current work, the dissociation of molecular nitrogen on W(110) has been studied using ab initio molecular dynamics (AIMD) calculations, simulating both surface temperature effects, such as lattice distortion, and surface motion effects, like recoil. The forces were calculated using density functional theory, and two density functionals were tested, namely the PBE and the RPBE functionals. The computed dissociation probability considerably differs from earlier static surface results, with AIMD predicting a much larger contribution of the indirect reaction channel, in which molecules dissociate after being temporally trapped in the proximity of the surface. Calculations suggest that the surface motion effects play a role here, since the energy transfer to the lattice does not allow molecules that have been trapped into potential wells close to the surface to find their way back to the gas ⇤ Email: f.nattino@chem.leidenuniv.nl 1 phase. In comparison to experimental data, AIMD results overestimate the dissociation probability at the lowest energies investigated, where trapping dominates, suggesting a failure of both tested exchange-correlation functionals in describing the potential energy surface in the area sampled by trapped molecules.

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“…In contrast, the relevance of this dissipation channel in gas-surface interactions that involve energies up to a few eV is not so clear. It depends not only on the specific system, but also on the elementary process considered, as shown by different studies on scattering [5][6][7][8][9][10][11][12] and adsorption [6,[13][14][15][16][17][18][19][20][21][22][23][24][25][26] of atoms and molecules on surfaces. Low-energy e-h pair excitations have been detected as chemicurrents on Schottky diode devices during the chemisorption of atomic and molecular species on metals [13][14][15].…”

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Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

et al. 2014

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We study the dynamics of transient hot H atoms on Pd(100) that originated from dissociative adsorption of H 2 . The methodology developed here, denoted AIMDEF, consists of ab initio molecular dynamics simulations that include a friction force to account for the energy transfer to the electronic system. We find that the excitation of electron-hole pairs is the main channel for energy dissipation, which happens at a rate that is five times faster than energy transfer into Pd lattice motion. Our results show that electronic excitations may constitute the dominant dissipation channel in the relaxation of hot atoms on surfaces. DOI: 10.1103/PhysRevLett.112.103203 PACS numbers: 68.43.-h, 34.35.+a, 34.50.Bw, 82.20.Gk Electron-hole (e-h) pair excitations are an unquestioned efficient energy drain in the interaction of fast atoms with solids and surfaces [1][2][3][4]. In contrast, the relevance of this dissipation channel in gas-surface interactions that involve energies up to a few eV is not so clear. It depends not only on the specific system, but also on the elementary process considered, as shown by different studies on scattering [5][6][7][8][9][10][11][12] and adsorption [6,[13][14][15][16][17][18][19][20][21][22][23][24][25][26] of atoms and molecules on surfaces. Low-energy e-h pair excitations have been detected as chemicurrents on Schottky diode devices during the chemisorption of atomic and molecular species on metals [13][14][15]. The correlation found between chemicurrent intensities and adsorption energies is a strong indication that a large fraction of the energy dissipated in both the dissociative and nondissociative adsorption processes is used to excite e-h pairs. However, this strongly contrasts with examples showing that the dissociative adsorption is reasonably well described within the electronically adiabatic approach, which neglects the coupling between electronic excitations and the nuclear motion [6,[18][19][20]23,25], and that the effect of electronic energy dissipation seems negligible [21,24,26]. Therefore, a question that is raised here is at what stage of the dissociative adsorption process e-h pair excitations do become relevant.In a typical adsorption event, the incoming gas species gain additional kinetic energy when entering the attractive adsorption well. In the particular case of dissociative adsorption, this energy gain can lead to the formation of so-called "hot" atoms or fragments, with energies much larger than the corresponding thermal energies of the substrate atoms. The formed hot species will then propagate along the surface until they dissipate the excess kinetic energy and finally accommodate at a stable adsorption position. This stage of the dissociative adsorption process, where the relevance of e-h pair excitations has been traditionally neglected, is the focus of the present work.In this Letter we show that while e-h pair excitation may not be relevant on the molecule-bond-breaking time scale, it is an efficient dissipative channel in the subsequent relaxation of the...

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Publisher’s Note: Competition between Electron and Phonon Excitations in the Scattering of Nitrogen Atoms and Molecules off Tungsten and Silver Metal Surfaces [Phys. Rev. Lett.108, 096101 (2012)]

Cited by 24 publications

References 0 publications

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

Vibrational deexcitation and rotational excitation of H2 and D2 scattered from Cu(111): Adiabatic versus non-adiabatic dynamics

N2 dissociation on W(110): An ab initio molecular dynamics study on the effect of phonons

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

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