The electronic structure of benzene adsorbed on Ag(111) studied by angle resolved photoemission

Dudde, R.; Frank, K. H.; Koch, E. E.

doi:10.1016/0039-6028(90)90447-g

Cited by 63 publications

(98 citation statements)

References 21 publications

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“…Our optB88-vdW binding energy of −0.60 eV lies close to the middle of the range of experimental estimates (−0.80 to −0.42 eV). 71,72,75,76 However, since DFT-D2 is faster than the optB88-vdW functional, which is computationally expensive for large unit cells (the computational cost depends on the number of FFT grid points, which is determined by the size of the simulation cell), and because this study necessitates a large number of geometry optimizations, we wanted to determine if the DFT-D2 45 semi-empirical dispersion correction would perform equally well. Table I illustrates that the binding energies computed with the two methods differed by not more than TABLE II.…”

Section: A Benchmarking Benzenementioning

confidence: 99%

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Miller

Simpson

Tymińska

et al. 2015

The Journal of Chemical Physics

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Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH3)2) and deactivating (NO2) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (Hhcp) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.

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Section: A Benchmarking Benzenementioning

confidence: 99%

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Miller

Simpson

Tymińska

et al. 2015

The Journal of Chemical Physics

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“…As a first example, we start with a small molecule: benzene (Bz). This molecule has been highly used and studied as an adsorbate on Ag(111) [42,49,50] and is considered a model system for larger hydrocarbons. Here, Bz is adsorbed in a flat configuration [49] at a distance of 2.96Å [9].…”

Section: From Simple To Complex Interfacesmentioning

confidence: 99%

Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

Ferri

Ambrosetti

Tkatchenko

2017

Phys. Rev. Materials

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Electronic charge rearrangements at interfaces between organic molecules and solid surfaces play a key role in a wide range of applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. It is common to utilize electrostatics and Pauli pushback to control the interface electronic properties, while the ubiquitous van der Waals (vdW) interactions are often considered to have a negligible direct contribution (beyond the obvious structural relaxation). Here, we apply a fully self-consistent Tkatchenko-Scheffler vdW density functional to demonstrate that the weak vdW interactions can induce sizable charge rearrangements at hybrid metal/organic systems (HMOS). The complex vdW correlation potential smears out the interfacial electronic density, thereby reducing the charge transfer in HMOS, changes the interface work functions by up to 0.2 eV, and increases the interface dipole moment by up to 0.3 Debye. Our results suggest that vdW interactions should be considered as an additional control parameter in the design of hybrid interfaces with the desired electronic properties.

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“…37,57,58,59,60,61 The size and complexity of the perylene molecule is between that of benzene and PTCDA. The structure of an adsorbed perylene monolayer is thought to be similar to that of a PTCDA layer.…”

Section: Introductionmentioning

confidence: 99%

First-principles study of the dipole layer formation at metal-organic interfaces

et al. 2010

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We study the dipole layer formed at metal-organic interfaces by means of first-principles calculations. Interface dipoles are monitored by calculating the work function change of Au, Ag, Al, Mg and Ca surfaces upon adsorption of a monolayer of PTCDA (3,4,9,10-perylene-tetra-carboxylic-dianhydride), perylene or benzene molecules. Adsorption of PTCDA leads to pinning of the work function for a range of metal substrates. It gives interface dipoles that compensate for the difference in the clean metal work functions, leading to a nearly constant work function. In contrast, adsorption of benzene always results in a decrease of the work function, which is relatively constant for all metal substrates. Both effects are found in perylene, where adsorption on low work function metals gives work function pinning, whereas adsorption on high work function metals gives work function lowering. The work function changes upon adsorption are analyzed and interpreted in terms of two competing effects. If the molecule and substrate interact weakly, the molecule pushes electrons into the surface, which lowers the work function. If the metal work function is sufficiently low with respect to the unoccupied states of the molecule, electrons are donated into these states, which increases the binding and the work function.

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The electronic structure of benzene adsorbed on Ag(111) studied by angle resolved photoemission

Cited by 63 publications

References 21 publications

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

Electronic charge rearrangement at metal/organic interfaces induced by weak van der Waals interactions

First-principles study of the dipole layer formation at metal-organic interfaces

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