Accounting for van der Waals interactions between adsorbates and surfaces in density functional theory based calculations: selected examples

Ramalho, J. P. Prates; Gomes, José R. B.; Illas, Francesc

doi:10.1039/c3ra40713f

Cited by 141 publications

(86 citation statements)

References 108 publications

(168 reference statements)

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“…The approach remains sophisticated due to the necessity to evaluate multidimensional integrals. For a comprehensive review of several dispersion correction methods, we refer to Ramalho et al [43].…”

Section: B Substrate Effects On Graphene Electronic Propertiesmentioning

confidence: 99%

Adsorption of alkali adatoms on graphene supported by the Au/Ni(111) surface

2015

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We study alkali-metal adsorption on supported graphene by means of density-functional-theory calculations that include dispersion corrections. Graphene supported by the Au/Ni(111) surface is an important system for fundamental studies because this surface allows one to support graphene, preserving the electronic properties of freestanding graphene. We investigate the binding energetics as well as the structural and electronic properties of Li, Na, K, and Rb atoms adsorbed or intercalated at the graphene/Au/Ni(111) interfaces and compare the results to those obtained on freestanding graphene. Both the adsorption and intercalation of the alkali atoms induce electron doping to the graphene π bands that display a quasirigid-energy shift. Electron doping by alkali atoms preserves the Dirac cone of graphene, which shifts downwards due to the negative polarity of the doping. The metallic or ionic character of the alkali dopant is controlled by its position relative to graphene. All of the investigated alkali atoms display an energetic preference to intercalate between graphene and the Au/Ni support. These results shed light on the relationship between graphene electron doping, the alkali-atom adsorption site, and the charge transfers at the graphene/support interface.

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Section: B Substrate Effects On Graphene Electronic Propertiesmentioning

confidence: 99%

Adsorption of alkali adatoms on graphene supported by the Au/Ni(111) surface

2015

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“…Interestingly, the inclusion of van der Waals interactions brings adsorption energies for different coverages closer to each other. We note that careful selection of the dispersion correction method is crucial as there are reports of frequent overestimation of van der Waals interaction energies [35]. 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].…”

Section: Adsorptionmentioning

confidence: 99%

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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“…38 The inclusion of dispersion corrections is expected to impact the magnitudes of the adsorption energies without changing the qualitative picture of the overall reaction.…”

Section: 2931mentioning

confidence: 99%

Methanol dissociation on bimetallic surfaces: validity of the general Brønsted–Evans–Polanyi relationship for O–H bond cleavage

2016

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Density functional theory (DFT) calculations were employed to study the dissociation of the O-H bond in methanol on several planar and stepped bimetallic transition metal surfaces, composed of elements showing high or moderate activity towards this reaction, namely, Ni, Rh, Ru, Ir, Pd, Au, Zn and Cu. The activation energies for the O-H bond cleavage were compared with those estimated using a Brønsted-Evans-Polanyi (BEP) relationship for the RO-H bond breakage on pure metal transition surfaces, relating the activation energy for the reaction with the adsorption energies of the reaction products, ROc and Hc adsorbed on the surface of the catalyst. Furthermore, the average differences between the values of the activation energies calculated with the exhaustive determination of the full reaction path and location of the transition state on each surface model and the activation energies obtained from the BEP relationship with the simple calculation of the adsorption energies of the ROc and Hc species are $0.14 eV. This suggests that the BEP relationship developed upon the consideration of data for dissociation of the O-H bond in alcohols and water on pure metal surfaces is also valid for a qualitative prediction of the methanol activation energy on bimetallic surfaces.

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Accounting for van der Waals interactions between adsorbates and surfaces in density functional theory based calculations: selected examples

Cited by 141 publications

References 108 publications

Adsorption of alkali adatoms on graphene supported by the Au/Ni(111) surface

Adsorption of alkali adatoms on graphene supported by the Au/Ni(111) surface

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

Methanol dissociation on bimetallic surfaces: validity of the general Brønsted–Evans–Polanyi relationship for O–H bond cleavage

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