Physisorption of helium on a TiO2(110) surface: Periodic and finite cluster approaches

Lara‐Castells, María Pilar de; Aguirre, Néstor F.; Mitrushchenkov, Alexander

doi:10.1016/j.chemphys.2011.07.013

Cited by 11 publications

(43 citation statements)

References 65 publications

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“…26 and references therein) we are aware of only one first-principle study on the He-TiO 2 (110)-(1×1) interaction. 27 This recent study has shown that periodic calculations using the Perdew-Burke-Ernzerhof (PBE) functional and an electronic basis set tailored to minimize the basis set superposition error, yield a short and medium-range interaction potential, as a function of the vertical height z above the most stable adsorption site, in very reasonable agreement with those obtained using correlated wavefunction-based methods and finite, hydrogen-terminated and embedded, model cluster approaches. In particular, the well-depth (84 cm −1 ) and the equilibrium distance (3.2 Å) obtained through periodic PBE calculations underestimated by less than 2% and 5%, respectively, the values evaluated at local Möller-Plesset second order perturbation (LMP2) level on the largest hydrogen-terminated cluster considered (of stoichiometry Ti 9 O 34 H 32 ).…”

Section: Introductionmentioning

confidence: 60%

“…Benchmark periodic MP2 calculations with the CRYSCOR code 30 on the He−MgO(100) interaction by Martinez-Casado et al 31 also revealed a good agreement between PBE and MP2 results for the well-depth (to within 0.3 meV). Similarly to the case of the He−TiO 2 (110) interaction, 27 these results showed the inability of the PBE approach to describe the long-range dispersive interaction and then the proper −1/z 3 asymptotic behaviour. This arises from the well-known fundamental problem of local and semilocal DFT functionals to capture the correct 1/R 6 dependence of the dispersion energy as a function of the distance R between the interacting fragments (see, e.g., for recent reviews Refs.…”

Section: Introductionmentioning

confidence: 69%

“…Likewise, the correlation energies calculated with a modified version 28 of the cluster-in-solid embedding technique 29 agreed with those obtained with a similar size hydrogen-terminated cluster within 10%, indicating the validity of the adopted hydrogen-saturated cluster models. 27 On the other hand, MP2 correlation energies calculated with the embedded cluster approach underestimated those evaluated using the more accurate coupled cluster theory through perturbative triples, CCSD(T), by less than 15%. Benchmark periodic MP2 calculations with the CRYSCOR code 30 on the He−MgO(100) interaction by Martinez-Casado et al 31 also revealed a good agreement between PBE and MP2 results for the well-depth (to within 0.3 meV).…”

Section: Introductionmentioning

confidence: 97%

“…38 The periodic DFT calculations reported in Ref. 27 were restricted to the potential regions falling around the minimum energy path. We have performed additional calculations on a dense three-dimensional grid to provide the necessary data for the fitting of the global He-surface PES.…”

Section: Introductionmentioning

confidence: 99%

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Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Aguirre

Mateo

Mitrushchenkov

et al. 2012

The Journal of Chemical Physics

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This paper is the first of a two-part series dealing with quantum-mechanical (density-functionalbased) studies of helium-mediated deposition of catalytic species on the rutile TiO 2 (110)-(1×1) surface. The interaction of helium with the TiO 2 (110)-(1×1) surface is first evaluated using the Perdew-Burke-Ernzerhof functional at a numerical grid dense enough to build an analytical three-dimensional potential energy surface. Three (two prototype) potential models for the He-surface interaction in helium scattering calculations are analyzed to build the analytical potential energy surface: (1) the hard-corrugated-wall potential model; (2) the corrugated-Morse potential model; and (3) the threedimensional Morse potential model. Different model potentials are then used to study the dynamics upon collision of a 4 He 300 cluster with the TiO 2 (110) surface at zero temperature within the framework of a time-dependent density-functional approach for the quantum fluid [D. Mateo, D. Jin, M. Barranco, and M. Pi, J. Chem. Phys. 134, 044507 (2011)] and classical dynamics calculations. The laterally averaged density functional theory-based potential with an added long-range dispersion interaction term is further applied. At variance with classical dynamics calculations, showing helium droplet splashing out of the surface at impact, the time evolution of the macroscopic helium wavefunction predicts that the helium droplet spreads on the rutile surface and leads to the formation of a thin film above the substrate. This work thus provides a basis for simulating helium mediated deposition of metallic clusters embedded within helium nanodroplets.

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Section: Introductionmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 69%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Aguirre

Mateo

Mitrushchenkov

et al. 2012

The Journal of Chemical Physics

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“…It has been applied to different problems of correlation in extended systems. [73][74][75][76][77] Special embedding based on orbital space partitioning has been also developed to deal with metal surfaces. 78 As an alternative to these embedding methods, DFT-based embedding theory has been extensively developed (see Refs.…”

Section: Introductionmentioning

confidence: 99%

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag2/graphene

Lara‐Castells

Mitrushchenkov

Stoll

2015

The Journal of Chemical Physics

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A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141, 151102 (2014)], is applied to describe the van der Waals dominated Ag2/graphene interaction. It extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster model (coronene), and ending with the periodic model of the extended system, modern ab initio methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected density functional-based approaches are put together both to assess the accuracy of the composite scheme and to better characterize the Ag2/graphene interaction. The present work illustrates how the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab initio-based schemes in extended systems for surface science applications.

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Adsorption of Noble-Gas Atoms on the TiO₂(110) Surface: An Ab Initio-Assisted Study with van der Waals-Corrected DFT

2016

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Weakly bound noble gases (Ne, Ar, Kr, and Xe) are being utilized as probes to monitor the photocatalytic activity of the TiO 2 (110) surface. In this work, this adsorption problem is examined using different van der Waals-corrected DFT-based treatments on periodic systems. The assessment of their performance is assisted by the application of nonperiodic DFT-based symmetry adapted perturbation theory [SAPT(DFT)]. It is further verified by comparing with experimentally based determinations of the adsorption energies at one-monolayer surface coverage. Besides being dispersion-dominated adsorbate/surface interactions, the SAPT(DFT)based decomposition reveals that the electrostatic and induction energy contributions become highly relevant for the heaviest noble-gas atoms (krypton and xenon). The most reliable results are provided by the revPBE-D3 approach: it predicts adsorption energies of −118.4, −165.8, and −2231.7 meV for argon, krypton, and xenon, which are within 6% of the experimental values, and attractive long-range tails which are consistent with our ab initio benchmarking. Moreover, the revPBE density functional describes the short-range part of the potential energy curve more precisely, avoiding the exchange-only binding effects of the PBE functional. The nonlocal vdW-DF2 density functional performs well at the long-range potential region but largely overestimates the adsorption energies of noble gas atoms as light as argon. The Tkatchenko−Scheffler dispersion correction combined with the revPBE functional produces accurate estimations of the adsorption energies (to within 10%) but long-range attractive tails that decay too slowly as in first-generation nonlocal vdW-DF density functional. Lateral interactions between coadsorbate atoms contribute up to about 15−20%, being key in achieving good agreement with experimental measurements. The interaction with the noble-gas atoms reduces the work function of the TiO 2 (110) surface, agreeing to the experimental observation of an inhibited photodesorption of coadsorbed molecular oxygen.

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Physisorption of helium on a TiO2(110) surface: Periodic and finite cluster approaches

Cited by 11 publications

References 65 publications

Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag2/graphene

Adsorption of Noble-Gas Atoms on the TiO₂(110) Surface: An Ab Initio-Assisted Study with van der Waals-Corrected DFT

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Physisorption of helium on a TiO2(110) surface: Periodic and finite cluster approaches

Cited by 11 publications

References 65 publications

Helium mediated deposition: Modeling the He−TiO2(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Helium mediated deposition: Modeling the He−TiO2(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag2/graphene

Adsorption of Noble-Gas Atoms on the TiO2(110) Surface: An Ab Initio-Assisted Study with van der Waals-Corrected DFT

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Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Helium mediated deposition: Modeling the He−TiO₂(110)-(1×1) interaction potential and application to the collision of a helium droplet from density functional calculations

Adsorption of Noble-Gas Atoms on the TiO₂(110) Surface: An Ab Initio-Assisted Study with van der Waals-Corrected DFT