Van der Waals effect in weak adsorption affecting trends in adsorption, reactivity, and the view of substrate nobility

Kelkkanen, André K.; Lundqvist, Bengt I.; Nørskov, Jens K.

doi:10.1103/physrevb.83.113401

Cited by 33 publications

(39 citation statements)

References 47 publications

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“…71 For this system, neither vdW-DF1 nor vdW-DF2 are able to predict the right balance between repulsive and attractive terms that results in the experimental finding of a weak chemisorption. 70 We find that vdW-DF1 predicts the best binding energies for both benzene and C60 on graphene.…”

Section: -76mentioning

confidence: 98%

Analysis of van der Waals density functional components: Binding and corrugation of benzene and C60on boron nitride and graphene

2013

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The adsorption of benzene and C60 on graphene and boron nitride (BN) is studied using density functional theory with the non-local correlation functional vdW-DF. By comparing these systems we can systematically investigate their adsorption nature and differences between the two functional versions vdW-DF1 and vdW-DF2. The bigger size of the C60 molecule makes it bind stronger to the surface than benzene, yet the interface between the molecules and the sheets are similar in nature. The binding separation is more sensitive to the exchange variant used in vdW-DF than to the correlation version. This result is related to the exchange and correlation components of the potential energy curve (PEC). We show that a moderate dipole forms for C60 on graphene, unlike for the other adsorption systems. We find that the corrugation is very sensitive to the variant or version of vdW-DF used, in particular the exchange. Further, we show that this sensitivity arise indirectly through the shift in binding separation caused by changing vdW-DF variant. Based on our results, we suggest a concerted theory-experiment approach to assess the exchange and correlation contributions to physisorption. Using DFT calculations, the corrugation can be linked to the optimal separation, allowing us to extract the exchange-correlation part of the adsorption energy. Molecules with same interfaces to the surface, but different geometries, can in turn cast light on the role of van der Waals forces.

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Section: -76mentioning

confidence: 98%

Analysis of van der Waals density functional components: Binding and corrugation of benzene and C60on boron nitride and graphene

2013

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“…[9][10][11] A large majority of previous theoretical work on vdW interactions mainly focused on weakly bound systems. [12][13][14][15][16][17][18] Typical examples include benzene (Bz) adsorbed on the Ag(111) and Au(111) surfaces, [15][16][17][18] and noble gases on the Cu(111), Ag(111), Pt(111), and Pd(111) surfaces. 10,[19][20][21] A unifying aspect of these studies is the observation that the inclusion of vdW interactions into standard DFT within the generalized gradient approximation (GGA) often brings a large increase in binding, and results in a much better agreement with experimental adsorption distances and energies.…”

Section: Introductionmentioning

confidence: 99%

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

et al. 2012

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The adsorption of aromatic molecules on metal surfaces plays a key role in condensed matter physics and functional materials. Depending on the strength of the interaction between the molecule and the surface, the binding is typically classified as either physisorption or chemisorption. Van der Waals (vdW) interactions contribute significantly to the binding in physisorbed systems, but the role of the vdW energy in chemisorbed systems remains unclear. Here we study the interaction of benzene with the (111) surface of transition metals, ranging from weak adsorption (Ag and Au) to strong adsorption (Pt, Pd, Ir, and Rh). When vdW interactions are accurately accounted for, the barrier to adsorption predicted by standard density-functional theory (DFT) calculations essentially vanishes, producing a metastable precursor state on Pt and Ir surfaces. Notably, vdW forces contribute more to the binding of covalently bonded benzene than they do when benzene is physisorbed.Comparison to experimental data demonstrates that some of the recently developed methods for including vdW interactions in DFT allow quantitative treatment of both weakly and strongly adsorbed aromatic molecules on metal surfaces, extending the already excellent performance found for molecules in the gas phase.

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“…The hybrid interfaces often consist of aromatic molecules and transition metal surfaces4567. Among these, closest-packed metal surfaces, in particular the (111) surface of face-centered cubic (FCC) lattices, were most extensively used, due to the low energy, high stability, and easy processability891011. However, for realistic applications the non-closest-packed surfaces are sometimes evitable and can be used in, for example, enantioselective separators, heterogeneous catalysis, and field-emitter displays12131415.…”

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confidence: 99%

Aromatic molecules on low-index coinage metal surfaces: Many-body dispersion effects

Jiang

Yang

et al. 2016

Sci Rep

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Understanding the binding mechanism for aromatic molecules on transition-metal surfaces in atomic scale is a major challenge in designing functional interfaces for to (opto)electronic devices. Here, we employ the state-of-the-art many-body dispersion (MBD) approach, coupled with density functional theory methods, to study the interactions of benzene with low-index coinage metal surfaces. The many-body effects contribute mostly to the (111) surface, and leastly to the (110) surface. This corresponds to the same sequence of planar atomic density of face-centered-cubic lattices, i.e., (111) > (100) > (110). The binding energy for benzene/Au(110) is even stronger than that for benzene/Ag(110), due to a larger broadening of molecular orbitals in the former case. On the other hand, our calculations show almost identical binding energies for benzene on Ag(111) and Au(111), which contradicts the classic d-band center theory that could well predict the trend in chemisorption energies for various small molecules on a number of metal surfaces. Our results provide important insight into the benchmark adsorption systems with opener surfaces, which could help in designing more complex functional interfaces.

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Van der Waals effect in weak adsorption affecting trends in adsorption, reactivity, and the view of substrate nobility

Cited by 33 publications

References 47 publications

Analysis of van der Waals density functional components: Binding and corrugation of benzene and C60on boron nitride and graphene

Analysis of van der Waals density functional components: Binding and corrugation of benzene and C60on boron nitride and graphene

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding

Aromatic molecules on low-index coinage metal surfaces: Many-body dispersion effects

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