Repulsion between molecules on a metal: Monolayers and submonolayers of hexa-<i>peri</i>-hexabenzocoronene on Au(111)

Wagner, Christian; Kasemann, Daniel; Golnik, C.; Forker, Roman; Esslinger, M.; Müllen, Kläus; Fritz, Torsten

doi:10.1103/physrevb.81.035423

Cited by 49 publications

(70 citation statements)

References 32 publications

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“…The molecular topography reflects the expected chemical structure of BN-HBC, and is in all aspects similar to that observed for unsubstituted HBC adsorbed on Au(111). [13] The measured electronic height of the molecule, 1.8 Å (Fig. 1c), is comparable with previous reports for other two-dimensional polyaromatic hydrocarbon molecules on a Au(111) surface.…”

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confidence: 78%

Construction of an Internally B₃N₃‐Doped Nanographene Molecule

et al. 2015

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Construction of an Internally B₃N₃‐Doped Nanographene Molecule

et al. 2015

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“…[39][40][41] Intermolecular repulsion can be also caused by Coulomb interaction between partially charged parts of molecules. 9 Another mechanism, by which interadsorbate repulsion can arise, is the formation of an electronic standing wave pattern between adsorbates, as has been suggested for pentacene/Cu(110). 42 This suggestion is based on the measurement of the Cu adatom distribution at low temperatures by Repp et al 43 that was explained in terms of Hyldgard-Persson theory.…”

Section: Discussion Of the Phase Behavior For θ < 1 ML T < 180 Kmentioning

confidence: 94%

Structure and growth of tetracene on Ag(111)

et al. 2011

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The structure of the tetracene/Ag(111) interface in the coverage range θ = 0 to 2.4 ML is studied with scanning tunneling microscopy (STM) at 8 K and with low energy electron diffraction (LEED) at T = 300 . . . 100 K. For θ 0.01 ML, one-dimensional (1D) diffusion of single molecules along 011 -directions is observed even at 8 K. For 0.1 ML < θ < 0.5 ML molecules are homogeneously distributed over the surface forming a disordered phase (static at T = 8 K, dynamic at T = 25 K), indicating a repulsive intermolecular interaction (δ-phase). For θ 0.5 ML, local ordering in the commensurate γ -phase is observed. Further increase of the coverage yields a compressed monolayer (ML) phase (θ ≡ 1 ML) with point-on-line registry (α-phase). The interaction between molecules has been calculated with the force-field approach to rationalize the molecular packing motifs in the various phases. Under most circumstances molecule-molecule interactions are repulsive, in agreement with experimental findings. A simulation of the adsorption up to θ = 1 ML according to the random sequential adsorption (RSA) algorithm shows that the disorder-to-order transition from the δ-to γ -phase occurs close to random close packing (RCP), θ = 0.5-0.6 ML. Since tetracene molecules are a two-dimensional (2D) representation of Onsager's hard rod model, this suggests that this phase transition is driven both energetically and entropically. For θ ≈ 2.23 ML a metastable bilayer phase with point-on-line coincidence is observed (β-phase). The basic structural unit of this phase is a triplet of molecules that are tilted along the long molecular axis against each other; at least one of these molecules is tilted out of the surface plane. Within the β-phase a superstructure of alternating rotation domains is observed. This superstructure has a period of 7.4 nm. The molecular packing in the β-phase resembles the packing in the bulk crystal structure of tetracene, its formation can therefore be interpreted as incipient pseudomorphic growth of tetracene on Ag(111). However, pseudomorphic growth cannot be continued beyond the β-phase.

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“…In fact, a recent quantum Monte Carlo study [53] of stable square ice between graphene sheets shows that most dispersion-corrected DFT functionals overestimate the binding in the water layer. Finally, the long-range repulsion between a quasi-3D oscillator dimer presented here may provide an alternate interpretation of lateral repulsion between monolayer structures of hexabenzocoronene on Au(111), where a 90% screening of the lateral vdW interactions by the surface was suggested previously [12].…”

Section: Prl 118 210402 (2017) P H Y S I C a L R E V I E W L E T T Ementioning

confidence: 98%

“…In fact, reported cases of longrange repulsion between physisorbed molecules abound in recent experimental literature [12][13][14][15][16]. The usual explanation attributes the repulsion to the charge transfer between the Fermi level of the metal surface and the molecular orbitals of the adsorbate [17] or the dominance of Pauli repulsion over a London-type dispersion interaction [18][19][20].…”

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Long-Range Repulsion Between Spatially Confined van der Waals Dimers

Sadhukhan

Tkatchenko

2017

Phys. Rev. Lett.

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It is an undisputed textbook fact that nonretarded van der Waals (vdW) interactions between isotropic dimers are attractive, regardless of the polarizability of the interacting systems or spatial dimensionality. The universality of vdW attraction is attributed to the dipolar coupling between fluctuating electron charge densities. Here, we demonstrate that the long-range interaction between spatially confined vdW dimers becomes repulsive when accounting for the full Coulomb interaction between charge fluctuations. Our analytic results are obtained by using the Coulomb potential as a perturbation over dipole-correlated states for two quantum harmonic oscillators embedded in spaces with reduced dimensionality; however, the longrange repulsion is expected to be a general phenomenon for spatially confined quantum systems. We suggest optical experiments to test our predictions, analyze their relevance in the context of intermolecular interactions in nanoscale environments, and rationalize the recent observation of anomalously strong screening of the lateral vdW interactions between aromatic hydrocarbons adsorbed on metal surfaces. DOI: 10.1103/PhysRevLett.118.210402 Interactions induced by quantum-mechanical charge density fluctuations, such as van der Waals (vdW) and Casimir forces, are always present between objects with finite dimensions [1][2][3][4]. Such interactions are important not only for many fundamental phenomena throughout the fields of biology, chemistry, and physics but also for the design and performance of micro-and nano-structured devices. While Casimir forces can be both attractive or repulsive, depending on the nature of the fluctuations (quantum and/or thermal) and the spatial structure (topology and/or geometry) of the interacting systems [5][6][7][8], it is undisputed common wisdom that nonretarded vdW interactions between two objects in vacuo are inherently attractive [9][10][11]. The universality of vdW attraction is attributed to the ubiquitous zero-point energy lowering, induced by dipolar coupling between fluctuating electron charge densities [9,10].However, many biological, chemical, and physical phenomena of importance in materials happen in spatially confined environments, as opposed to isotropic and homogeneous vacuum. The confinement can be artificially engineered by applying static or dynamic electromagnetic fields or arise as a result of the encapsulation of molecules in nanotubes, fullerenes, and/or by adsorption on polarizable surfaces. Moreover, in biological systems, proteins are typically confined in an inhomogeneous environment. We remark that even when such confinement entails tiny modification of the electron density (having no apparent effect on the electrostatics), it can visibly affect the interactions stemming from density fluctuations due to their long-range inhomogeneous nature.Here, we demonstrate that the breaking of rotational and/or translational symmetry of 3D vacuum results in repulsive long-range interactions for vdW dimers.The repulsive interaction stems from...

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Repulsion between molecules on a metal: Monolayers and submonolayers of hexa-peri-hexabenzocoronene on Au(111)

Cited by 49 publications

References 32 publications

Construction of an Internally B₃N₃‐Doped Nanographene Molecule

Construction of an Internally B₃N₃‐Doped Nanographene Molecule

Structure and growth of tetracene on Ag(111)

Long-Range Repulsion Between Spatially Confined van der Waals Dimers

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Repulsion between molecules on a metal: Monolayers and submonolayers of hexa-peri-hexabenzocoronene on Au(111)

Cited by 49 publications

References 32 publications

Construction of an Internally B3N3‐Doped Nanographene Molecule

Construction of an Internally B3N3‐Doped Nanographene Molecule

Structure and growth of tetracene on Ag(111)

Long-Range Repulsion Between Spatially Confined van der Waals Dimers

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Construction of an Internally B₃N₃‐Doped Nanographene Molecule

Construction of an Internally B₃N₃‐Doped Nanographene Molecule