RPBE-vdW Description of Benzene Adsorption on Au(111)

Wellendorff, Jess; Kelkkanen, André K.; Mortensen, Jens Jørgen; Lundqvist, Bengt I.; Bligaard, Thomas

doi:10.1007/s11244-010-9443-6

Cited by 59 publications

(61 citation statements)

References 29 publications

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“…However, the use of the relaxed DFT-PBE geometries [i.e., approach (b)] determines a larger molecule-surface distance of 2.87Å and a slightly lower adsorption energy of E vdW-DF ads = −735 meV. An adsorption energy of only −137 meV from our DFT-PBE calculations for a single thiophene on Cu(111) would be characteristic for a physisorbed system such as benzene on Au(111) 44,45 where the molecule does not form chemical bonds to the surface. However, in our case the charge density difference plots suggest a weak chemisorption bonding process.…”

Section: Dft-d3 Adsmentioning

confidence: 99%

Semiempirical van der Waals interactions versusab initiononlocal correlation effects in the thiophene-Cu(111) system

et al. 2012

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The adsorption mechanism of single thiophene (C 4 H 4 S), 4-thiophene (C 16 H 10 S 4 ), and their dimers on the Cu(111) surface has been studied in the framework of the density functional theory (DFT). The importance of the London dispersion effects on the molecule-surface adsorption geometry and the corresponding binding energy was investigated by using semiempirical and first-principles methods. Interestingly, the physisorption character of the thiophene bonding on Cu(111) suggested by strength of the molecule-surface interaction as revealed by the DFT calculations turns out to be a weak chemisorption even for the DFT ground-state geometry when a nonlocal correlation energy functional [Dion et al., Phys. Rev. Lett. 92, 246401 (2004)] is used. Our ab initio calculations also suggest that the formation of thiophene and 4-thiophene dimers is energetically favorable with respect to the adsorption of single molecules.

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Section: Dft-d3 Adsmentioning

confidence: 99%

Semiempirical van der Waals interactions versusab initiononlocal correlation effects in the thiophene-Cu(111) system

et al. 2012

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“…As such, it is outside the scope of local approximations to density functional theory, and modeling van der Waals interactions using nonlocal functionals is a topic of ongoing research. [64][65][66] In contrast to this, the preceding treatment of screening, in conjunction with a full many-body treatment of the π-electrons on the molecule, makes it possible to calculate the π-electron contribution to van der Waals interaction straightforwardly with no extra adjustable parameters.…”

Section: π-Electron Contribution To the Van Der Waals Interactionmentioning

confidence: 99%

Effective field theory of interactingπelectrons

2012

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We develop a π-electron effective field theory (π-EFT) wherein the two-body Hamiltonian for a π-electron system is expressed in terms of three effective parameters: the π-orbital quadrupole moment, the on-site repulsion, and a dielectric constant. As a first application of this π-EFT, we develop a model of screening in molecular junctions based on image multipole moments, and use this to investigate the reduction of the HOMO-LUMO gap of benzene. Beyond this, we also use π-EFT to calculate the differential conductance spectrum of the prototypical benzenedithiol-Au single-molecule junction and the π-electron contribution to the van der Waals interaction between benzene and a metallic electrode.

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“…[9][10][11] A large majority of previous theoretical work on vdW interactions mainly focused on weakly bound systems. [12][13][14][15][16][17][18] Typical examples include benzene (Bz) adsorbed on the Ag(111) and Au(111) surfaces, [15][16][17][18] and noble gases on the Cu(111), Ag(111), Pt(111), and Pd(111) surfaces. 10,[19][20][21] A unifying aspect of these studies is the observation that the inclusion of vdW interactions into standard DFT within the generalized gradient approximation (GGA) often brings a large increase in binding, and results in a much better agreement with experimental adsorption distances and energies.…”

Section: Introductionmentioning

confidence: 99%

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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RPBE-vdW Description of Benzene Adsorption on Au(111)

Cited by 59 publications

References 29 publications

Semiempirical van der Waals interactions versusab initiononlocal correlation effects in the thiophene-Cu(111) system

Semiempirical van der Waals interactions versusab initiononlocal correlation effects in the thiophene-Cu(111) system

Effective field theory of interactingπelectrons

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

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