Modified Shepard interpolation of gas-surface potential energy surfaces with strict plane group symmetry and translational periodicity

Frankcombe, Terry J.; Collins, Michael A.; Zhang, Dong H.

doi:10.1063/1.4757149

Cited by 39 publications

(36 citation statements)

References 63 publications

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“…Future work to improve the fit to the DFT data is foreseen and underway. Future improvement will involve inclusion of AIMD trajectory based DFT data in the fit and may implement alternative fitting methods, for example, neural networks [55][56][57] and modified Shepard interpolation [58]. Ultimately, comparisons to experimental scattering data may help refine the PES.…”

Section: Discussionmentioning

confidence: 99%

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Janke

Pavanello

Kroes

et al. 2013

Zeitschrift Für Physikalische Chemie

234

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We report an analytic potential energy surface (PES) based on several hundred DFT energies for H interacting with a Au(111) surface. Effective medium theory is used to fit the DFT data, which were obtained for the Au atoms held at their equilibrium positions. This procedure also provides an adequate treatment of the PES for displacements of Au atoms that occur during scattering of H atoms. The fitted PES is compared to DFT energies obtained from ab initio molecular dynamics trajectories. We present molecular dynamics simulations of energy and angle resolved scattering probabilities at five incidence angles at an incidence energy, E i = 5 eV, and at a surface temperature, T S = 10 K. Simple single bounce trajectories are important at all incidence conditions explored here. Double bounce events also make up a significant fraction of the scattering. A qualitative analysis of the double-bounce events reveals that most occur as collisions of an H-atom with two neighboring surface gold atoms. The energy losses observed are consistent with a simple binary collision model, transferring typically less than 150 meV to the solid per bounce.

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Section: Discussionmentioning

confidence: 99%

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Janke

Pavanello

Kroes

et al. 2013

Zeitschrift Für Physikalische Chemie

234

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“…128,188,189 A comparison of detailed scattering results obtained for H 2 + Cu (111) to results obtained using the ''gold standard'' method (the CRP method) shows that the MS method is accurate enough to allow a good description of the results that are very sensitive to the PES used, for instance, rotational excitation and diffraction probabilities. This problem should now be solved thanks to a recent work by Frankcombe et al, 256 which shows how plane group symmetry can be imposed. This problem should now be solved thanks to a recent work by Frankcombe et al, 256 which shows how plane group symmetry can be imposed.…”

Section: Potential Surface Fittingmentioning

confidence: 99%

Quantum and classical dynamics of reactive scattering of H₂ from metal surfaces

2016

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We review the state-of-the art in dynamics calculations on the reactive scattering of H2 from metal surfaces, which is an important model system of an elementary reaction that is relevant to heterogeneous catalysis. In many applications, quantum dynamics and classical trajectory calculations are performed within the Born-Oppenheimer static surface model. However, ab initio molecular dynamics (AIMD) is finding increased use in applications aimed at modeling the effect of surface phonons on the dynamics. Molecular dynamics with electronic friction has been used to model the effect of electron-hole pair excitation. Most applications are still based on potential energy surfaces (PESs) or forces computed with density functional theory (DFT), using a density functional within the generalized gradient approximation to the exchange-correlation energy. A new development is the use of a semi-empirical version of DFT (the specific reaction parameter (SRP) approach to DFT). We also discuss the accurate methods that have become available to represent electronic structure data for the molecule-surface interaction in global PESs. It has now become possible to describe highly activated H2 + metal surface reactions with chemical accuracy using the SRP-DFT approach, as has been shown for H2 + Cu(111) and Cu(100). However, chemical accuracy with SRP-DFT has yet to be demonstrated for weakly activated systems like H2 + Ru(0001) and non-activated systems like H2 + Pd(111), for which SRP DFs are not yet available. There is now considerable evidence that electron-hole pair (ehp) excitation does not need to be modeled to achieve the (chemically) accurate calculation of dissociative chemisorption and scattering probabilities. Dynamics calculations show that phonons can be safely neglected in the chemically accurate calculation of sticking probabilities on cold metal surfaces for activated systems, and in the calculation of a number of other observables. However, there is now sufficient evidence to suggest that the decision on whether or not to neglect phonons should be taken with care, with appropriate consideration of the observable to be computed and of the relevant surface temperature. AIMD calculations have provided valuable insights into the mechanisms that are operative in the dissociative adsorption and absorption of hydrogen on/in precovered metal surfaces. Classical and quantum dynamics calculations have shown that the reaction probability of H2 on Pt surfaces consisting of (100) steps and (111) terraces can to a very good approximation be computed as a weighted average of the reactivities on the steps and terraces. Progress obtained with dynamics calculations on the scattering of H2 from alloys and from simple low index metal surfaces is also reported. Insights that may be obtained on the reactivity of a metal surface from the prominent presence of out-of-plane diffraction or, conversely, the complete absence of diffraction, are discussed. A new field has been opened up by experiments on H2 scattering from surfaces at fast graz...

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“…55 Each potential energy surface has p3m1 symmetry. 56 As a consequence, a distinction can be made between second and third layer hollow sites, called HCP and FCC, respectively (see Figure 3). PESs have been calculated for 4 different exchange-correlation functionals: Perdew, Burke, and Ernzerhof (PBE), 57 RPBE, 58 PBE-vdW-DF (denoted hereafter by PBE-vdW), 57,59 and PBEα-vdW-DF.…”

Section: B Electronic Structure Methodsmentioning

confidence: 99%

Towards a specific reaction parameter density functional for reactive scattering of H2 from Pd(111)

Boereboom

Wijzenbroek

Somers

et al. 2013

The Journal of Chemical Physics

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Recently, an implementation of the specific reaction parameter (SRP) approach to density functional theory (DFT) was used to study several reactive scattering experiments of H2 on Cu(111). It was possible to obtain chemical accuracy (1 kcal/mol ≈ 4.2 kJ/mol), and therefore, accurately model this paradigmatic example of activated H2 dissociation on a metal surface. In this work, the SRP-DFT methodology is applied to the dissociation of hydrogen on a Pd(111) surface, in order to test whether the SRP-DFT approach is also applicable to non-activated H2-metal systems. In the calculations, the Born-Oppenheimer static surface approximations are used. A comparison to molecular beam sticking experiments, performed at incidence energies ≥125 meV, on H2 + Pd(111) suggested the PBE-vdW [where the Perdew, Burke, and Ernzerhof (PBE) correlation is replaced by van der Waals correlation] functional as a candidate SRP density functional describing the reactive scattering of H2 on Pd(111). Unfortunately, quantum dynamics calculations are not able to reproduce the molecular beam sticking results for incidence energies <125 meV. From a comparison to initial state-resolved (degeneracy averaged) sticking probabilities it seems clear that for H2 + Pd(111) dynamic trapping and steering effects are important, and that these effects are not yet well modeled with the potential energy surfaces considered here. Applying the SRP-DFT method to systems where H2 dissociation is non-activated remains difficult. It is suggested that a density functional that yields a broader barrier distribution and has more non-activated pathways than PBE-vdW (i.e., non-activated dissociation at some sites but similarly high barriers at the high energy end of the spectrum) should allow a more accurate description of the available experiments. Finally, it is suggested that new and better characterized molecular beam sticking experiments be done on H2 + Pd(111), to facilitate the development of a more accurate theoretical description of this system.

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Modified Shepard interpolation of gas-surface potential energy surfaces with strict plane group symmetry and translational periodicity

Cited by 39 publications

References 63 publications

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Quantum and classical dynamics of reactive scattering of H₂ from metal surfaces

Towards a specific reaction parameter density functional for reactive scattering of H2 from Pd(111)

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Modified Shepard interpolation of gas-surface potential energy surfaces with strict plane group symmetry and translational periodicity

Cited by 39 publications

References 63 publications

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface

Quantum and classical dynamics of reactive scattering of H2 from metal surfaces

Towards a specific reaction parameter density functional for reactive scattering of H2 from Pd(111)

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Quantum and classical dynamics of reactive scattering of H₂ from metal surfaces