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Goikoetxea, Itziar; Juaristi, J. I.; Muiño, R. Dı́ez; Alducin, M.

doi:10.1103/physrevlett.113.066103

Cited by 38 publications

(44 citation statements)

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“…Note that a similar adsorption geometry has been found on both Fe(110) [56] and Fe/W(110) [57], but the adsorption energy is larger on W(110). Note also the rather extended bond length of the adsorbed molecules with respect to the gas-phase value (about 20% longer).…”

Section: Molecular Adsorption Statesmentioning

confidence: 51%

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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Section: Molecular Adsorption Statesmentioning

confidence: 51%

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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“…As prototypical examples from catalysis, the dissociation probability of N 2 molecules over iron varies by order of magnitudes, decreasing from (111) to (100) and (110) crystal faces at low gas pressure. 3 Simulations of molecular beam experiments on Fe(111) 4 and Fe(110) 5,6 also exhibit this trend for N 2 adsorption. Large effects are also experimentally and theoretically observed in the initial sticking probability of N 2 on tungsten surfaces [7][8][9][10] and O 2 on the three low-index crystal faces of silver.…”

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confidence: 89%

Communication: Hot-atom abstraction dynamics of hydrogen from tungsten surfaces: The role of surface structure

Galparsoro

Busnengo

Juaristi

et al. 2017

The Journal of Chemical Physics

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Adiabatic and non-adiabatic quasiclassical molecular dynamics simulations are performed to investigate the role of the crystal face on hot-atom abstraction of H adsorbates by H scattering from covered W(100) and W(110). On both cases, hyperthermal diffusion is strongly affected by the energy dissipated into electron-hole pair excitations. As a result, the hot-atom abstraction is highly reduced in favor of adsorption at low incidence energy and low coverages, i.e., when the mean free path of the hyperthermal H is typically larger. Qualitatively, this reduction is rather similar on both surfaces, despite at such initial conditions, the abstraction process involves more subsurface penetration on W(100) than on W(110).

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“…In this system, the six-dimensional (6D) PES calculated within the frozen-surface approximation features two molecular adsorption minima at the top (local minimum) and hollow (global minimum) sites, where the N-N bond lies perpendicular and parallel to the surface, respectively [29,31]. Remarkably, if relaxation of Fe atoms is allowed, a new molecular adsorption local minimum appears at the surface bridge site with parallel orientation (see Fig.…”

mentioning

confidence: 99%

“…In contrast to N/Ag(111), we do not observe a fast kinetic energy gain upon the approach of the projectile to the surface. The reason is the presence of energy barriers at z ∼ 2.5Å [29,31] that the molecules have to overcome before accessing the adsorption wells. As a result, we observe a drop of E A K starting at t = 0 that is the combined effect of an increase of the potential energy and of energy transfer to the surface lattice.…”

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confidence: 99%

Ab initiomolecular dynamics with simultaneous electron and phonon excitations: Application to the relaxation of hot atoms and molecules on metal surfaces

et al. 2015

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The relaxation dynamics of hot H, N, and N 2 on Pd(100), Ag(111), and Fe(110), respectively, is studied by means of ab initio molecular dynamics with electronic friction. This method is adapted here to account for the electron density changes caused by lattice vibrations, thus treating on an equal footing both electron-hole (e-h) pair and phonon excitations. We find that even if the latter increasingly dominate the heavier is the hot species, the contribution of e-h pairs is by no means negligible in these cases because it gains relevance at the last stage of the relaxation process. The quantitative details of energy dissipation depend on the interplay of the potential energy surface, electronic structure, and kinetic factors. DOI: 10.1103/PhysRevB.92.201411 PACS number(s): 82.65.+r, 34.35.+a, 34.50.Bw, 68.43.−h In dynamic gas-surface environments, where gas-phase atomic and molecular species impinge on the surface at energies of the order of up to a few eV, energy dissipation occurs by the excitation of electron-hole (e-h) pairs and the excitation of lattice vibrations, i.e., phonons [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. In the adsorption processes of atomic and molecular species, dissociative as well as nondissociative, the species trapped by the surface gradually lose their energy until they become thermalized on the surface. The competition between the e-h pairs and phonon channels governs the relaxation dynamics of the transient hot species, and thus it plays a decisive role in the system reactivity properties. The reason is that it rules the traveled length and relaxation time of a hot atom or molecule on the surface and, consequently, the probability to undergo a recombination reaction with another adsorbate [18][19][20][21][22][23].Recent ab initio molecular dynamics (AIMD) simulations with electronic friction (AIMDEF) have shown that e-h pair excitations are the dominant relaxation mechanism for hot H atoms on Pd(100) that originate from the dissociative adsorption of H 2 [16]. More particularly, this channel dissipates energy at a five times faster rate than the phonon channel [10]. The two main reasons behind this behavior are the long H-Pd interaction time, of hundreds of fs, and the low adsorbate-tosurface atom mass ratio, γ = m H /m Pd = 0.0094. The case of H on Pd(100) represents a limiting case. For heavier adsorbates, the relative weight of e-h pairs and phonons in the energy loss is expected to vary. The energy transfer to the substrate will be determined not only by kinetic factors, such as the value of γ and the incidence conditions, but also by the topography of the multidimensional potential energy surface (PES) and the electronic structure details of the configurations probed along the relaxation trajectory.In this Rapid Communication, we investigate the relaxation dynamics of hot species in three adsorption scenarios that are representative of different energy loss regimes. We have chosen atomic N on Ag(111) (γ = 0.13), N 2 on Fe(110) (γ = 0.5), and the aforemen...

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Surface Strain Improves Molecular Adsorption but Hampers Dissociation forN2on theFe/W(

Cited by 38 publications

References 42 publications

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

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

Communication: Hot-atom abstraction dynamics of hydrogen from tungsten surfaces: The role of surface structure

Ab initiomolecular dynamics with simultaneous electron and phonon excitations: Application to the relaxation of hot atoms and molecules on metal surfaces

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