Adding Pieces to the CO/Pt(111) Puzzle: The Role of Dispersion

Janthon, Patanachai; Viñes, Francesc; Sirijaraensre, Jakkapan; Limtrakul, Jumras; Illas, Francesc

doi:10.1021/acs.jpcc.7b00365

Cited by 60 publications

(55 citation statements)

References 61 publications

(147 reference statements)

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“…The interaction of CO with metal surfaces is known to be challenging to reproduce quantitatively with DFT [68][69][70] , and therefore we performed a sensitivity analysis to understand the effect of the binding strength of CO on the population of different Pd structures (i.e., Pd monomers, Pd-Pd dimers, and Pd trimers) ( Supplementary Fig. S8).…”

Section: Resultsmentioning

confidence: 99%

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

et al. 2021

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The atomic scale structure of the active sites in heterogeneous catalysts is central to their reactivity and selectivity. Therefore, understanding active site stability and evolution under different reaction conditions is key to the design of efficient and robust catalysts. Herein we describe theoretical calculations which predict that carbon monoxide can be used to stabilize different active site geometries in bimetallic alloys and then demonstrate experimentally that the same PdAu bimetallic catalyst can be transitioned between a single-atom alloy and a Pd cluster phase. Each state of the catalyst exhibits distinct selectivity for the dehydrogenation of ethanol reaction with the single-atom alloy phase exhibiting high selectivity to acetaldehyde and hydrogen versus a range of products from Pd clusters. First-principles based Monte Carlo calculations explain the origin of this active site ensemble size tuning effect, and this work serves as a demonstration of what should be a general phenomenon that enables in situ control over catalyst selectivity.

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Section: Resultsmentioning

confidence: 99%

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

et al. 2021

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“…27,28 In particular the accurate first-principles description of molecule-metal interfaces in general is not trivial due to the formation of dipole layers in this region, which is particularly important in case of SAMs. [62][63][64][67][68][69][70][71][72][73][74]…”

Section: Opti N Wiresmentioning

confidence: 99%

Toward a First-Principles Evaluation of Transport Mechanisms in Molecular Wires

Kröncke

Herrmann

2020

J. Chem. Theory Comput.

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Understanding charge transport through molecular wires is important for nanoscale electronics and biochemistry. Our goal is to establish a simple first-principles protocol for predicting the charge transport mechanism in such wires, in particular the crossover from coherent tunneling for short wires to incoherent hopping for longer wires. This protocol is based on a combination of density-functional theory with a polarizable continuum model introduced by Kaupp et al. for mixed-valence molecules, which we had previously found to work well for length-dependent charge delocalization in such systems. We combine this protocol with a new charge delocalization measure tailored for molecular wires, and we show that it can predict the tunneling-to hopping transition length with a maximum error of one subunit in five sets of molecular wires studied experimentally in molecular junctions at room temperature. This suggests that the protocol is also well suited for estimating the extent of hopping sites as relevant, e.g., for the intermediate tunneling-hopping regime in DNA. File list (3) download file view on ChemRxiv ms.pdf (1.59 MiB) download file view on ChemRxiv supporting_information.pdf (3.90 MiB) download file view on ChemRxiv cartesian_coordinates.zip (33.23 KiB)

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“…Many previous studies showed that the hollow adsorption site is preferred by these semilocal approximations, while the low-coordination top site is preferred in the experiments. A recent study by Janthon et al 17 reported that the semi-empirical M06-L meta-GGA predicts both correct adsorption site and adsorption energy. Sun et al 18 showed that a revised version (revTPSS) of the TPSS meta-GGA significantly improves the surface energies and adsorption energies for transition metals.…”

Section: Introductionmentioning

confidence: 99%

Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors

et al. 2019

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Adsorption of the molecule CO on metallic surfaces is an important unsolved problem in Kohn-Sham density functional theory (KS-DFT). We present a detailed study of carbon monoxide adsorption on fcc (111) surfaces of 3d, 4d and 5d metals using nonempirical semilocal density functionals for the exchange-correlation energy: the local-density approximation (LDA), two generalized gradient approximations or GGAs (PBE and PBEsol), and a meta-GGA (SCAN). The typical error pattern (as found earlier for free molecules and for free transition metal surfaces), in which results improve from LDA to PBE or PBEsol to SCAN, due to the satisfaction of more exact constraints, is not found here. Instead, for CO adsorption on transition metal surfaces, we find that, while SCAN overbinds much less than LDA, it overbinds slightly more than PBE. Moreover, the tested functionals often predict the wrong adsorption site, as first pointed out for LDA and GGA in the CO/Pt (111) puzzle. This abnormal pattern leads us to suspect that the errors of PBE and SCAN for this problem are density-driven self-interaction errors associated with incorrect charge transfer between molecule and metal surface. We point out that, by the variational principle, overbinding by an approximate functional would be reduced if that functional were applied not to its selfconsistent density for the adsorbed system but to an exact or more correct density for that system. Finally, we show for CO on Pt(111) that the site preference is corrected and the adsorption energy is improved for the PBE functional by using not the selfconsistent PBE density but a PBE+U density. The resulting correction to the PBE total energy is much larger for the adsorbed system than for its desorbed components, showing that the error is in the density of the adsorbed system. This seems to solve the Feibelman 2001 CO/Pt(111) puzzle, in principle if not fully in practice. arXiv:1807.05450v2 [cond-mat.mtrl-sci]

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Adding Pieces to the CO/Pt(111) Puzzle: The Role of Dispersion

Cited by 60 publications

References 61 publications

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

Directing reaction pathways via in situ control of active site geometries in PdAu single-atom alloy catalysts

Toward a First-Principles Evaluation of Transport Mechanisms in Molecular Wires

Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors

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