Long-Range Repulsive Interaction between Molecules on a Metal Surface Induced by Charge Transfer

Fernández-Torrente, I.; Monturet, Serge; Franke, Katharina J.; Fraxedas, Jordi; Lorente, Nicolás; Pascual, José

doi:10.1103/physrevlett.99.176103

Cited by 175 publications

(192 citation statements)

References 31 publications

(37 reference statements)

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“…For a slightly higher coverage (θ > 0.5 ML), a uniform compression of the intermolecular distance is not observed in experiments, a scenario indicative of direct molecule-molecule interaction such as dipole-dipole 66 or electrostatic 67 repulsion. Rather, CoPc molecules form one-dimensional chains (Figure 1(i)), indicating that the surface state is essential in the structure formation of CoPc on Cu(111).…”

Section: Copc On Cu(111)mentioning

confidence: 91%

Review Article: Structures of phthalocyanine molecules on surfaces studied by STM

Wang¹,

Wu²,

Berndt³

2012

AIP Advances

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This review mainly focuses on progress recently achieved in the growth of phthalocyanine molecules on single-crystal surfaces of sub-monolayer up to few-monolayer thin films studied by scanning tunneling microscopy in our groups. On metallic surfaces such as Au(111), Ag(111) and Cu(111), molecular superstructures are determined by combining directional intermolecular interactions caused by symmetry reduction, molecule-substrate interactions and indirect long-range interactions due to quantum interference of surface state electrons. On semiconducting TiO2 surface, molecular assembling structures are dictated by the strong molecule-substrate interaction. However, on insulating NaCl film, molecule-molecule interaction dominates over the molecule-NaCl coupling, leading to molecular growth behavior. Knowledge obtained from these studies would help people better understand the physicochemical properties of the phthalocyanine molecules at surfaces so that their new applications could be further explored and uncovered in the future

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Section: Copc On Cu(111)mentioning

confidence: 91%

Review Article: Structures of phthalocyanine molecules on surfaces studied by STM

Wang¹,

Wu²,

Berndt³

2012

AIP Advances

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“…5 Another example is tetrathiafulvalene (TTF) which acquires a considerable dipole moment out of the film plane of nearly 5 D on Au(111). 20 In this paper, we will analyze several factors that contribute to the self-assembly of ZI on metal surfaces, including chemical bond formation, epitaxial considerations, dipolar interactions, and substrate-mediated long-range interactions. We will show that the structure formation on surfaces is mainly driven by a competition between intermolecular interactions and molecule-substrate interactions.…”

Section: Introductionmentioning

confidence: 99%

Self-assembly of strongly dipolar molecules on metal surfaces

Kunkel

Hooper

Simpson

et al. 2015

The Journal of Chemical Physics

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The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C 6 H 2 (· · · NHR) 2 (· · · O) 2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings. C 2015 AIP Publishing LLC. [http://dx

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“…At the adsorbate-metal interface several physical and chemical phenomena such as hybridization [1] and charge transfer [2] may strongly affect the behaviour of the adsorbed molecular entities. New strategies to tune the characteristics of the adsorbate-surface interface are thus intensively explored [3], but only few studies have examined the directly related consequences on the electronic properties of the molecular adsorbates themselves.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of bimolecular islands on ultrathin NaCl films by a vicinal substrate

et al. 2009

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a b s t r a c tThe structure of ultrathin NaCl films on Au(1 1 1) and on Au(11 12 12), as well as the one of bimolecular 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) and 1,4-bis-(2,4-diamino-1,3,5,-triazine)-benzene (BDATB) islands on NaCl films on both surfaces have been studied with a low-temperature scanning tunnelling microscope. We show that intermixed bimolecular assemblies based on selective three-fold hydrogen-bonding (H-bonding), that have previously been observed on Au(1 1 1) and on Au(11 12 12), can also be stabilized on insulating NaCl films on Au, however, only if these films are grown on Au(11 12 12) and not on Au(1 1 1). The behaviour of the heterocomplex structures is found to be largely influenced by the structural properties of the underlying substrate and by the number of NaCl layers. On a partly NaCl-covered Au(1 1 1) surface, the excess of molecules after completion of the first layer on Au prefers to form a second molecular layer based on ordered heterocomplex structures rather than to adsorb on the NaCl islands. The use of a vicinal surface together with the strong cohesion characteristic of the NaCl film introduces smooth elastic deformations on the NaCl(0 0 1) plane. As a consequence, the periodically modified structure of the overlayer provides preferential binding sites and allows adsorption of two-dimensional molecular structures. In contrast to what is observed on Au(11 12 12), the molecular domains on the NaCl film do not follow the Au step directions, but the NaCl(0 0 1) high symmetry directions. Our results provide a strategy to increase the adsorption energy of flat molecules on insulating layers by choosing a vicinal metal substrate.

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Long-Range Repulsive Interaction between Molecules on a Metal Surface Induced by Charge Transfer

Cited by 175 publications

References 31 publications

Review Article: Structures of phthalocyanine molecules on surfaces studied by STM

Review Article: Structures of phthalocyanine molecules on surfaces studied by STM

Self-assembly of strongly dipolar molecules on metal surfaces

Stabilization of bimolecular islands on ultrathin NaCl films by a vicinal substrate

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