Vertical bonding distances of PTCDA on Au(111) and Ag(111): Relation to the bonding type

Henze, S.K.M.; Bauer, Oliver; Lee, T.-L.; Sokołowski, M.; Tautz, F. Stefan

doi:10.1016/j.susc.2007.01.020

Cited by 149 publications

(182 citation statements)

References 35 publications

(82 reference statements)

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“…Note that although the coverage of the two (three) DIP films prepared on each substrate was not identical, we did not observe a significantly coverage-dependent bonding distance d H . Comparing these results with the bonding distances of PTCDA on the same metal surfaces, i.e., d H = 2.66Å on Cu(111), 16 d H = 2.86Å on Ag(111), 15,16 , and d H = 3.27Å on Au(111), 17 we see that the bonding distances follow the same order, i.e., d H …”

Section: A Experimental Resultsmentioning

confidence: 68%

“…For Cu(111) we thus find (2.51 ± 0.03)Å, and for Ag(111) (3.01 ± 0.04)Å. Due to the reconstruction of the Au(111) surface, which results in a 3% larger spacing between the first and second Au layers, 17 the bonding distance decreases from the measured apparent value (3.17 ± 0.03)Å to (3.10 ± 0.03)Å. All experimental results are summarized in Table I.…”

Section: A Experimental Resultsmentioning

confidence: 72%

“…[12][13][14] With respect to its chemical structure, DIP is a relatively simple, planar hydrocarbon without heteroatoms. In contrast to the intensely studied perylene derivative [15][16][17][18][19][20] 3,4,9,10-perylene tetracarboxylic dianhydrid (PTCDA, C 32 H 8 O 6 ) with its four keto groups, the DIP-substrate interaction is not complicated by polar side groups, and the influence of intermolecular interactions is expected to be smaller than for PTCDA. 21 Here, we present a systematic study with high-precision experimental data and state-of-the-art calculations of DIP adsorbed on Cu(111), Ag(111), and Au(111).…”

Section: Introductionmentioning

confidence: 94%

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Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

et al. 2013

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We present a benchmark study for the adsorption of a large π -conjugated organic molecule on different noble metal surfaces, which is based on x-ray standing wave (XSW) measurements and density functional theory calculations with van der Waals (vdW) interactions. The bonding distances of diindenoperylene on Cu(111), Ag(111), and Au (111) surfaces (2.51, 3.01, and 3.10Å, respectively) determined with the normal-incidence XSW technique are compared with calculations. Excellent agreement with the experimental data, i.e., deviations less than 0.1Å, is achieved using the Perdew-Burke-Ernzerhof (PBE) functional with vdW interactions that include the collective response of substrate electrons (the PBE + vdW surf method). It is noteworthy that the calculations show that the vdW contribution to the adsorption energy increases in the order Au(111) < Ag(111) < Cu(111).

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Section: A Experimental Resultsmentioning

confidence: 68%

Section: A Experimental Resultsmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 94%

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Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

et al. 2013

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“…In fact, in the case of PTCDA our calculated distance of 3.3 Å is now much closer to the experimental one of 3.27 Å . 68 Overall, atomic displacements within the molecules are not larger than 0.01 Å . Note that because the revPBE exchange tends to give longer bond lengths, 71 we may expect that our molecule-to-surface distances are slightly overestimated.…”

Section: Molecules and Dimers On Surfacesmentioning

confidence: 92%

Role of van der Waals interaction in forming molecule-metal junctions: flat organic molecules on the Au(111) surface

Mura

Guļāns

Thonhauser

et al. 2010

Phys. Chem. Chem. Phys.

115

147

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The self-assembly of flat organic molecules on metal surfaces is controlled, apart from the kinetic factors, by the interplay between the molecule-molecule and molecule-surface interactions. These are typically calculated using standard density functional theory within the generalized gradient approximation, which significantly underestimates nonlocal correlations, i.e. van der Waals (vdW) contributions, and thus affects interactions between molecules and the metal surface in the junction. In this paper we address this question systematically for the Au(111) surface and a number of popular flat organic molecules which form directional hydrogen bonds with each other. This is done using the recently developed first-principles vdW-DF method which takes into account the nonlocal nature of electron correlation [M. Dion et al., Phys. Rev. Lett. 2004, 92, 246401]. We report here a systematic study of such systems involving completely self-consistent vdW-DF calculations with full geometry relaxation. We find that the hydrogen bonding between the molecules is only insignificantly affected by the vdW contribution, both in the gas phase and on the gold surface. However, the adsorption energies of these molecules on the surface increase dramatically as compared with the ordinary density functional (within the generalized gradient approximation, GGA) calculations, in agreement with available experimental data and previous calculations performed within approximate or semiempirical models, and this is entirely due to the vdW contribution which provides the main binding mechanism. We also stress the importance of self-consistency in calculating the binding energy by the vdW-DF method since the results of non-self-consistent calculations in some cases may be off by up to 20%. Our calculations still support the usually made assumption of the molecule-surface interaction changing little laterally suggesting that single molecules and their small clusters should be quite mobile at room temperature on the surface. These findings support a gas-phase modeling for some flat metal surfaces, such as Au(111), and flat molecules, at least as a first approximation.

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“…It is known that the interaction between PTCDA and Au(111) is rather weak. 55,[118][119][120][121][122] For consistency with previous work, 70 our calculations use the same geometry as in Ref. 122, where dispersion-corrected functionals yield excellent agreement with the experiment for the structure, and 3 layers of Au (111) are used to represent the slab; a 2 × 2 × 1 k-mesh (1 × 1 × 1 for the Fock exchange contribution) is employed.…”

Section: Ptcda On Au(111)mentioning

confidence: 92%

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

Liu

Egger

Refaely-Abramson

et al. 2017

The Journal of Chemical Physics

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The alignment of the frontier orbital energies of an adsorbed molecule with the substrate Fermi level at metal-organic interfaces is a fundamental observable of significant practical importance in nanoscience and beyond. Typical density functional theory calculations, especially those using local and semi-local functionals, often underestimate level alignment leading to inaccurate electronic structure and charge transport properties. In this work, we develop a new fully self-consistent predictive scheme to accurately compute level alignment at certain classes of complex heterogeneous molecule-metal interfaces based on optimally tuned range-separated hybrid functionals. Starting from a highly accurate description of the gas-phase electronic structure, our method by construction captures important nonlocal surface polarization effects via tuning of the long-range screened exchange in a range-separated hybrid in a non-empirical and system-specific manner. We implement this functional in a plane-wave code and apply it to several physisorbed and chemisorbed molecule-metal interface systems. Our results are in quantitative agreement with experiments, for both the level alignment and work function changes. Our approach constitutes a new practical scheme for accurate and efficient calculations of the electronic structure of molecule-metal interfaces.

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Vertical bonding distances of PTCDA on Au(111) and Ag(111): Relation to the bonding type

Cited by 149 publications

References 35 publications

Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

Role of van der Waals interaction in forming molecule-metal junctions: flat organic molecules on the Au(111) surface

Energy level alignment at molecule-metal interfaces from an optimally tuned range-separated hybrid functional

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