Influence of supercell size on Gas-Surface Scattering: A case study of CO scattering from Au(1 1 1)

Hu, Ce; Lin, Qidong; Guo, Hua; Jiang, Bin

doi:10.1016/j.chemphys.2021.111423

Cited by 12 publications

(12 citation statements)

References 75 publications

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“…84 (A more accurate and higherdimensional fit was later developed using EANN. 85 ) Our PES identified not only a physisorption well, as in an earlier study, 82 but also a chemisorption well, with comparable well depths. The chemisorbed CO with a C-down configuration is much closer to the surface, thus amenable to strong nonadiabatic coupling with EHPs.…”

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confidence: 89%

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First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity

Zhou

Meng

Guo

et al. 2022

J. Phys. Chem. Lett.

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Energy transfer is ubiquitous during molecular collisions and reactions at gas−surface interfaces. Of particular importance is vibrational energy transfer because of its relevance to bond forming and breaking. In this Perspective, we review recent firstprinciples studies on vibrational energy-transfer dynamics during molecular scattering from metal surfaces at the state-to-state level. Taking several representative systems as examples, we highlight the intrinsic correlation between vibrational energy transfer in nonreactive scattering and surface reactivity and how it operates in both electronically adiabatic and nonadiabatic pathways. Adiabatically, the presence of a dissociation barrier softens a bond in the impinging molecule and increases its couplings with other molecular modes and surface phonons. In the meantime, the stronger interaction between the molecule and the surface also changes the electronic structure at the barrier, resulting in an increase of nonadiabatic effects. We further discuss future prospects toward a more quantitative understanding of this important surface dynamical process.

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confidence: 89%

“…To understand the scattering, trapping, diffusion, and desorption of the vibrationally excited CO molecule on Au(111), we have constructed a 60-dimensional BPNN PES based on DFT data . (A more accurate and higher-dimensional fit was later developed using EANN but also a chemisorption well, with comparable well depths.…”

Section: H2 Scattering From Metal Surfacesmentioning

confidence: 99%

First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity

Zhou

Meng

Guo

et al. 2022

J. Phys. Chem. Lett.

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“…The positions and momenta of surface atoms were first sampled from an NVT simulation with an Anderson thermostat . After equilibration of ∼3 ps, the simulation at the desired temperature was run for 10 ps, from which surface configurations were saved for the later QCT calculations.…”

Section: Methodsmentioning

confidence: 99%

“…The positions and momenta of surface atoms were first sampled from an NVT simulation with an Anderson thermostat. 46 After equilibration of ∼3 ps, the simulation at the desired temperature was run for 10 ps, from which surface configurations were saved for the later QCT calculations. The impinging H 2 (v = 0, j = 0) was simulated along the surface normal within a circle centered at the Pt site with a radius of r = 1.4 Å, since the reactivity drops to zero outside the circle due to the high barrier at Cu sites, as discussed in our previous work.…”

Section: Iib Qct and Qct-efmentioning

confidence: 99%

Short- and Long-Time Dynamics of Hydrogen Spillover from a Single Atom Platinum Active Site to the Cu(111) Host Surface

Jiang

et al. 2022

J. Phys. Chem. C

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Dynamics of the dissociative chemisorption of H2 (D2) and the subsequent H* (D*) diffusion on the Pt doped Cu(111) surface are investigated using both quasi-classical trajectory (QCT) and ring polymer molecular dynamics (RPMD) approaches. The classical dynamics is also studied with electronic friction to simulate the nonadiabatic interaction with surface electron–hole pairs. These dynamics calculations were made possible by a high-dimensional potential energy surface, machine learned from density functional theory data. It is shown that the diffusion of adsorbed H* at moderate temperatures can be largely characterized by classical mechanics, as evidenced by roughly the same diffusion coefficients obtained from QCT and RPMD calculations. In the long-time limit, the diffusion coefficient computed by averaging classical trajectories with electronic friction is in reasonably good agreement with the latest experimental data, underscoring the importance of the nonadiabatic interaction for H* diffusion on metal surfaces.

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“…The kinetics and dynamics of vibrational energy transfer of CO interacting with Au(111) have also attracted much interest, − serving as a comparative example to the NO + Au(111) system. Vibrational excitation of CO ( v = 0 → 1) and multi-quantum vibrational relaxation of CO ( v i = 17) scattered from Au(111) have been observed. − However, vibrational inelasticity of CO on Au(111) is much less remarkable, which seems to be consistent with an electron-mediated nonadiabatic mechanism. − In this respect, the much smaller electron binding energy of CO than NO suggests that electron transfer from the metal to CO is less favorable, resulting in much weaker nonadiabatic energy loss in the former case …”

Section: Introductionmentioning

confidence: 99%

Vibrational Relaxation of Highly Vibrationally Excited Molecules Scattered from Au(111): Role of the Dissociation Barrier

Meng

Jiang

2022

J. Phys. Chem. C

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Energy transfer during molecular collisions at a metal surface represents a sensitive probe of the molecule−surface interaction potential. Here, via molecular dynamics calculations on several first-principles neural network potentials, we find that the vibrational energy transfer dynamics of highly vibrationally excited NO and CO molecules scattered from Au(111) are strongly correlated with their respective potential energy landscapes in the vicinity of the dissociation barrier. Our results not only reproduce the observed significantly less vibrational relaxation of CO (v i = 17) than NO (v i = 16) scattered from Au(111) and attribute it to the different dissociation barriers in the two systems, but also show a dramatic change of dynamics due to a minor adjustment of the energy landscape near the barrier in the CO case. We find that the BEEF-vdW density functional based potential largely overestimates the vibrational relaxation of CO (v i = 17) even in the absence of any nonadiabatic energy loss, despite its good description for CO adsorption on Au(111). We also discuss the possibility of integrating the validated adiabatic potential with first-principles determined diabatic states towards a more complete description of the non-adiabatic energy transfer in these benchmark systems.

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Influence of supercell size on Gas-Surface Scattering: A case study of CO scattering from Au(1 1 1)

Cited by 12 publications

References 75 publications

First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity

First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity

Short- and Long-Time Dynamics of Hydrogen Spillover from a Single Atom Platinum Active Site to the Cu(111) Host Surface

Vibrational Relaxation of Highly Vibrationally Excited Molecules Scattered from Au(111): Role of the Dissociation Barrier

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