Density Functional Theory Analysis of Benzene (De)hydrogenation on Pt(111):  Addition and Removal of the First Two H-Atoms

Saeys, Mark; Reyniers, Marie Françoise; Neurock, Matthew; Marin, Guy

doi:10.1021/jp022166n

Cited by 75 publications

(102 citation statements)

References 96 publications

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“…1). This result is consistent with previous periodic slab GGA calculations, [40][41][42][43][44] as well as low-energy electron diffraction (LEED) 45 and scanning tunneling microscopy (STM) 46 experiments. Moreover, the PES shows a corrugation of 1.33 eV for Bz/Pt(111) when using PBE + vdW surf .…”

Section: Resultssupporting

confidence: 92%

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

et al. 2012

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The adsorption of aromatic molecules on metal surfaces plays a key role in condensed matter physics and functional materials. Depending on the strength of the interaction between the molecule and the surface, the binding is typically classified as either physisorption or chemisorption. Van der Waals (vdW) interactions contribute significantly to the binding in physisorbed systems, but the role of the vdW energy in chemisorbed systems remains unclear. Here we study the interaction of benzene with the (111) surface of transition metals, ranging from weak adsorption (Ag and Au) to strong adsorption (Pt, Pd, Ir, and Rh). When vdW interactions are accurately accounted for, the barrier to adsorption predicted by standard density-functional theory (DFT) calculations essentially vanishes, producing a metastable precursor state on Pt and Ir surfaces. Notably, vdW forces contribute more to the binding of covalently bonded benzene than they do when benzene is physisorbed.Comparison to experimental data demonstrates that some of the recently developed methods for including vdW interactions in DFT allow quantitative treatment of both weakly and strongly adsorbed aromatic molecules on metal surfaces, extending the already excellent performance found for molecules in the gas phase.

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Section: Resultssupporting

confidence: 92%

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

et al. 2012

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“…Our experiment, however, does not confirm the existence of this offset. We note that, for benzene adsorption on Pt(111), other adsorption heats, which are closer to the experimental value (but still much lower), have been computed (in kJ/mol): 132, 28 117, 29 104, 30 and 102. 31 The fact that all these studies underestimate the heat of adsorption suggests fundamental problems connected with DFT calculations for aromatic hydrocarbons adsorbed on metal surfaces.…”

Section: Discussionsupporting

confidence: 78%

“…The horizontal bars show further computed benzene adsorption energies. [28][29][30][31] terraces on Cu(111), 36 we attribute this to step edges. We conclude that the adsorption heat on steps (g331 kJ/mol) is >10% higher than the initial adsorption heat on terrace sites (∼300 kJ/mol).…”

Section: Discussionmentioning

confidence: 99%

Heat of Adsorption of Naphthalene on Pt(111) Measured by Adsorption Calorimetry

et al. 2006

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The heat of adsorption of naphthalene on Pt(111) at 300 K was measured with single-crystal adsorption calorimetry. The heat of adsorption on the ideal, defect-free surface is estimated to be (300 -34Θ -199Θ 2 ) kJ/mol. From this, a C-Pt bond energy for aromatic hydrocarbons on Pt(111) of ∼30 kJ/mol is estimated, consistent with earlier results for benzene on Pt(111). There is higher heat of adsorption at very low coverage, attributed to step sites where the adsorption heat is g330 kJ/mol. Saturation coverage, Θ ) 1 ML, corresponds to 1.55 × 10 14 molecules/cm 2 . Sticking probability measurements of naphthalene on Pt (111) give a high initial value of 1.0 and a Kisliuk-type coverage dependence that implies precursor-mediated sticking. The ratio of the hopping rate to the desorption rate of this precursor is ∼51. Naphthalene adsorbs transiently on top of chemisorbed naphthalene molecules with a heat of adsorption of 83-87 kJ/mol.

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“…[41,42] Further computational details concerning the use of metal clusters to simulate a surface can be found in previous publications. [14,23,15,18,19,12] The simulations of the extended Pt surface, modelled by a Pt slab with PBC, were carried out with the cp2k [43] program package. The selected simulation box shown in Figure 1 contains 144 atoms distributed on four layers (6 6 unit cells) exposing the (111) crystallographic plane.…”

Section: Methodsmentioning

confidence: 99%

“…The two terms give opposite contributions, since the distortion of the molecule causes a destabilization, while the adsorption to the metal improves the stability of the system. [19] This can be expressed by Equation (4):…”

Section: Decomposition Of the Adsorption Energymentioning

confidence: 99%

Adsorption of Naphthalene and Quinoline on Pt, Pd and Rh: A DFT Study

et al. 2008

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The adsorption of naphthalene and quinoline on Pt(111), Pd(111) and Rh(111) surfaces is studied using density functional theory. The metal surfaces are simulated by means of large confined clusters and for Pt by means of a slab with periodic boundary conditions (PBC). Calculation parameters such as basis set convergence, basis set superposition error and effects of cluster relaxation and size are analyzed in order to assess the aptness of the cluster model. For all the metals, the preferred sites of adsorption are analyzed, thus revealing their different behaviors concerning structure and stability of adsorption modes. On Pt, the molecules have the richest theoretical configurational variety. Naphthalene and quinoline are found to adsorb preferentially on di-bridge[7] sites on the three metals, and Rh exhibits higher adsorption energies than Pt and Pd. Structural features of the adsorbed molecules are correlated to the calculated adsorption energies. The di-bridge[7] adsorption modes are studied in deeper detail decomposing the adsorption energies in two terms arising from molecular distortion and binding interaction to the metal. Molecular distortion is correlated to the HOMO-LUMO energy gap. The larger adsorption energies found for interactions with Rh result from the lower contribution of the distortion term. Binding interactions are described by analyzing the wave functions of naphthalene and quinoline adsorbed on a subunit of the large clusters in order to reduce the complexity of the analysis. Molecular orbitals are studied using concepts of Frontier Molecular Orbitals theory. This approach reveals that in the adsorption of naphthalene and quinoline on Pt and Pd, an antibonding state lies below the Fermi energy, while on Rh all antibonding states are empty, in agreement with the larger interaction energies. In addition, further insight is gained by projecting the density of states on the d band of the clean surfaces and of the adsorbed systems. This results in the rationalization of the structural features in terms of the concepts of electronic structure theory. The distributions of electronic density are described by means of Hirshfeld charges and isosurfaces of differential electron density. The net electron transfer from the metals to the molecules for most of the sites correlates with the trends of the adsorption energies.

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Density Functional Theory Analysis of Benzene (De)hydrogenation on Pt(111): Addition and Removal of the First Two H-Atoms

Cited by 75 publications

References 96 publications

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

Heat of Adsorption of Naphthalene on Pt(111) Measured by Adsorption Calorimetry

Adsorption of Naphthalene and Quinoline on Pt, Pd and Rh: A DFT Study

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