Laser induced thermal desorption of carbon monoxide from Fe(110) surfaces

Wedler, G.; Ruhmann, H

doi:10.1016/0039-6028(82)90255-2

Cited by 171 publications

(24 citation statements)

References 18 publications

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“…However, recent benchmarking density functional studies show that the molecular adsorption on metal is generally described correctly with van der Waals techniques such as the Grimme's method used here [36][37][38]. A direct comparison with experiment to confirm the accuracy of the van der Waals technique used is not possible due to the fact that the only available early experiment results, with adsorption energy estimates in the 1-2 eV range, [12,39,40] are not site-specific and not accurate enough to allow us to distinguish results at the ∼10 meV scale necessary here. Once the CO molecule is adsorbed on the surface, it decomposes into surface-adsorbed C and O atoms and the C atom diffuses into the Fe surface to complete the carburization process.…”

Section: Adsorptionmentioning

confidence: 99%

“…Recent studies on 100 [10] and 111 [11] surfaces also show similar adsorption and dissociation energies. However, a number of experiments suggest CO is adsorbed on the 110 surface at low tem-perature with dissociation taking place at higher temperatures with an onset observed at at least 380 K [8,12]. Therefore with a barrier of 1.5 eV, CO dissociation on a clean Fe surface has only a negligible probability from a thermal activation perspective.…”

Section: Introductionmentioning

confidence: 99%

“…None of these later studies, however, used a dilute coverage with a focus on the electronic mechanisms of the adsorption and dissociation of CO as isolated processes. In earlier first-principles and experimental studies, 0.25 ML was the lowest coverage studied [5,7,[10][11][12]26]. Only higher coverages were studied due to the fact that onset of carburization was postulated at a dense hydrocarbon environment that represents a high carbon activity (a c > 1).…”

Section: Introductionmentioning

confidence: 99%

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Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

Chakrabarty

Bouhali

Mousseau

et al. 2016

Journal of Applied Physics

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Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface, that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band (CI-NEB) method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, Cinsertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from finite-size effects.

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Section: Adsorptionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

Chakrabarty

Bouhali

Mousseau

et al. 2016

Journal of Applied Physics

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“…[1][2][3] Laserinduced thermal desorption (LITD) was investigated in detail for the systems of CO/Fe(110) (Ref. 4) and Xe/Cu, 5 and has been successfully applied to the studies of surface diffusion combined with low-energy electron microscopy 6 or with scanning tunneling microscopy. 7 Nonthermal photostimulated phenomena, on the other hand, provide us with pathways that are nonaccessible in a thermal process.…”

Section: Introductionmentioning

confidence: 99%

Photostimulated desorption of Xe from Au(001) surfaces via transient Xe−formation

et al. 2011

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Photostimulated desorption (PSD) of Xe atoms from the Au(001) surface in thermal and nonthermal regimes was investigated by the time-of-flight measurement at photon energies of 6.4 and 2.3 eV. Xe was desorbed in a thermal way at high laser fluence, which was in good agreement with theoretical simulations. At a low laser fluence, on the other hand, desorption was induced only at a photon energy of 6.4 eV by a nonthermal one-photon process. We argue that the nonthermal PSD occurs via transient formation of Xe − on Au(001). The lifetime of Xe − is estimated to be ∼15 fs with a classical model calculation. Whereas the electron affinity of Xe is negative in the isolated state, it is stabilized by the metal proximity effect.

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“…6, X = 0.00159 and T = 1.1 s. The series of sharp dips in intensity at later times is due to laser-induced desorption [21,22] as UV is turned on for 1 s at different powers. As the UV is again switched off, diffracted intensity recovers by re-adsorption.…”

Section: Kinetics Of Adsorption/condensationmentioning

confidence: 98%