Quantification of finite-temperature effects on adsorption geometries of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mi>π</mml:mi></mml:math>-conjugated molecules: Azobenzene/Ag(111)

Mercurio, Giuseppe; Maurer, Reinhard J.; Liu, Wei; Hagen, Sebastian; Leyssner, Felix; Tegeder, Petra; Meyer, John‐Jules Ch.; Tkatchenko, Alexandre; Soubatch, Serguei; Reuter, Karsten; Tautz, F. Stefan

doi:10.1103/physrevb.88.035421

Cited by 47 publications

(60 citation statements)

References 43 publications

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“…In the case of PBE+vdW surf , this happens even though the metallic substrate response has already been effectively accounted for in the dispersion parameters. As it has also been shown for the case of azobenzene adsorbed to Ag(111), neglecting this effect leads to even further overestimation of adsorption energies and adsorption heights 31 . The remaining deviations to experiment, for example the overestimation of the adsorption interaction, may be ascribed to missing many-body dispersion contributions and the semi-local treatment of exchange interactions, both of which we will discuss below.…”

Section: Resultsmentioning

confidence: 92%

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Many-body dispersion effects in the binding of adsorbates on metal surfaces

Maurer

Ruiz

Tkatchenko

2015

The Journal of Chemical Physics

101

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A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic-inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Phys. Rev. Lett. 108, 236402 (2012); J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid (PTCDA), and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate-surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.

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Section: Resultsmentioning

confidence: 92%

“…Accounting for the latter by effective renormalization of metal C 6 coefficients, as done in the vdW surf scheme, 30 has improved adsorbate geometries significantly 31 , albeit at a remaining overbinding in adsorption energies.…”

Section: Introductionmentioning

confidence: 99%

Many-body dispersion effects in the binding of adsorbates on metal surfaces

Maurer

Ruiz

Tkatchenko

2015

The Journal of Chemical Physics

101

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“…Incorporated into selfassembled monolayers, molecular switches can be used to make functionalized surfaces, the macroscopic properties of which can be altered by changing the state of the switches [2][3][4]. Furthermore, many molecular switches are organic compounds and physisorb on metallic surfaces which makes them interesting to benchmark developments in density functional theory that include corrections to account for dispersive van der Waals-interactions [5][6][7].…”

Section: Introductionmentioning

confidence: 99%

Photo-induced and thermal reactions in thin films of an azobenzene derivative on Bi(111)

Bronner

Tegeder

2014

New J. Phys.

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Azobenzene is a prototypical molecular switch which can be interconverted with UV and visible light between a trans and a cis isomer in solution. While the ability to control their conformation with light is lost for many molecular photoswitches in the adsorbed state, there are some examples for successful photoisomerization in direct contact with a surface. However, there the process is often driven by a different mechanism than in solution. For instance, photoisomerization of a cyano-substituted azobenzene directly adsorbed on Bi(111) occurs via electronic excitations in the substrate and subsequent charge transfer.In the present study we observe two substrate-mediated trans-cis photoisomerization reactions of the same azobenzene derivative in two different environments within a multilayer thin film on Bi(111). Both processes are associated with photoisomerization and one is around two orders of magnitude more efficient than the other. Furthermore, the cis isomers perform a thermally induced reaction which may be ascribed to a back-isomerization in the electronic ground state or to a phenyl ring rotation of the cis isomer.Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 3 New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 4 New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 5 New J. Phys. 16 (2014) 053004 C Bronner and P Tegeder 7

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“…To elucidate the possible role of fluctuations, both thermal and induced by electronic correlations, we have chosen to study azobenzene in its planar form (AB) adsorbed on the Ag(111) surface -a widely used model for on-surface molecular switches ( Fig. 1a and b) [20,21]. Azobenzene is a challenging, but also ideal benchmark system containing all relevant features of realistic adsorbates: potential flexibility, low-frequency vibrational modes, and both covalent and dispersion-dominated binding motifs [22].…”

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Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111)

et al. 2016

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We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C 12 H 10 N 2 on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of manybody dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 10 24 s −1 that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems. DOI: 10.1103/PhysRevLett.116.146101 Complex molecules adsorbed at inorganic surfaces spark interest as basic building blocks in surface nanotechnology and energy materials [1], but also in the context of biocompatibility of biomolecule-metal interfaces and the structure of solid-liquid interfaces [2]. Considerable effort goes into characterizing the structure, stability, and dynamics of these systems [3]. In fact, with recent advances in experimental characterization techniques [4] and ab initio methods based on density-functional theory (DFT) [5], several systems have been well characterized at idealized conditions, i.e., low temperature and ultrahigh vacuum. These include planar aromatic molecules, such as benzene [6] and 3,4,9,10-perylene-tetracarboxylic acid (PTCDA) [7][8][9][10] adsorbed on the Ag(111) surface. Both examples represent comparably rigid molecules forming wellordered overlayer structures.In contrast, more complex adsorbed systems such as large polymer chains or biological molecules will be neither well ordered nor rigid. Their flexibility arises from internal torsions and rovibrational coupling in combination with long-range correlations and entails dynamics and reactivity that might be largely shaped by nontrivial thermal and electronic fluctuations. Whereas the role of thermal fluctuations and corresponding entropic contributions has always been at the forefront in the modeling of soft condensed matter, their relevance in gas-surface dynamics of flexible molecules in contact with inorganic surfaces is less clear.Long-range correlations induced by electronic fluctuations are an additional complication in the combined moleculesurface system. Several recent works have emphasized the role of temperature in the dynamics of benzene on stepped surfaces [11], the conformational switching of porphyrine derivatives on Cu(111) [12,13], and also in the thermal...

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Quantification of finite-temperature effects on adsorption geometries ofπ-conjugated molecules: Azobenzene/Ag(111)

Cited by 47 publications

References 43 publications

Many-body dispersion effects in the binding of adsorbates on metal surfaces

Many-body dispersion effects in the binding of adsorbates on metal surfaces

Photo-induced and thermal reactions in thin films of an azobenzene derivative on Bi(111)

Thermal and Electronic Fluctuations of Flexible Adsorbed Molecules: Azobenzene on Ag(111)

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