The role of exchange-correlation functionals in the potential energy surface and dynamics of N2 dissociation on W surfaces

Bocan, G. A.; Muiño, R. Dı́ez; Alducin, M.; Busnengo, H. F.; Salin, A.

doi:10.1063/1.2897757

Cited by 49 publications

(88 citation statements)

References 40 publications

(51 reference statements)

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“…These values are in good agreement with the low-temperature experimental value of 3.163 Å [39] and with the previous calculations from Alducin et al [12] and Bocan et al [15].…”

Section: Methodssupporting

confidence: 82%

“…[12,15], we find an adsorption well for N 2 placed above the top site at about 2.7 Å from the surface with the bond oriented perpendicular to the surface plane (top-vertical configuration). The adsorption energies that we determine for this configuration with PBE (0.621 eV) and RPBE (0.385 eV) reasonably reproduce the values from Refs.…”

Section: Molecular Adsorption Statesmentioning

confidence: 96%

“…Note that our computational setup is essentially the same as in Refs. [12,15], with only small differences in the k-point grids and energy cut-offs for the plane wave expansion, the use of PAW pseudopotentials instead of ultrasoft pseudopotentials and the use of the PBE functional instead of the PW91 [22,23] functional. Note, however, that the PBE functional has been designed to reproduce PW91 energies [49].…”

Section: Methodsmentioning

confidence: 99%

“…The bump is caused by the dissociation of molecules that are temporally trapped in the proximity of the surface, due to the energy transfer from the molecules' normal translational component to other molecular degrees of freedom (dynamic trapping). A different PES, which was computed with a different GGA density functional, the RPBE functional [24], produced better agreement for normal incidence, but dramatically failed at describing the reactivity at 60 incidence angle [15], with the majority of the molecules being scattered at large distance from the surface (about 3 Å). The authors concluded that the PW91-PES is less accurate close to the surface, in the area where the dissociation takes place, while the RPBE-PES is too repulsive at larger distances from the surface.…”

Section: Introductionmentioning

confidence: 99%

“…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%

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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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“…These values are in good agreement with the low-temperature experimental value of 3.163 Å [39] and with the previous calculations from Alducin et al [12] and Bocan et al [15].…”

Section: Methodssupporting

confidence: 82%

Section: Molecular Adsorption Statesmentioning

confidence: 96%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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Nitrogen Atom Abstraction of Nitrogen Chemisorbed on W(100) Surface

Ree

Kim

et al. 2018

Bulletin Korean Chem Soc

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We have computed the probability of N2 formation and the partitioning of the reaction exothermic energy of the product N2 molecule in the reaction N(g) + N(ad)/W → N2(g) + W. The N2 formation probability at the on‐top sites of the W(100) surface is approximately 0.01 at a gas temperature of 1800 K and surface temperature of 300 K. The total cross‐section of N2 formation at the on‐top sites of the W(100) surface as a function of the collision energy is significantly smaller than that at the hollow sites of the W(100) surface. The majority of the reaction energy is shared by the vibrational and translational motions of the newly produced N2. The vibrational excitations of the adsorbed nitrogen atom from the ground state to the higher levels 1, 2, and 3, do not significantly alter the energy shared by the product. In addition, strong vibrational excitation in N2 causes population inversion for the vibrational population. The energy transferred to the heat bath is negative, which denotes an energy transfer from the surface to the desorbed product. While the N2 formation probabilities do not depend significantly on the surface temperature (0–1500 K), they depend strongly on the gas temperature, which is consistent with the Eley‐Rideal reaction.

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