First-principles surface reaction rates by ring polymer molecular dynamics and neural network potential: role of anharmonicity and lattice motion

Li, Chen; Li, Yongle; Jiang, Bin

doi:10.1039/d2sc06559b

Cited by 4 publications

(3 citation statements)

References 91 publications

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“…87 Another new development in this eld has been the emergence of RPMD methods for describing gas-surface dynamics, such as recent work by Guo and coworkers, 88 who have studied H 2 dissociative chemisorption on Ag (111) and Pt (111), where this trajectory-based approach provides an easy way to study quantum effects related to tunneling over the dissociative barrier. Also, Li et al 89 have used RPMD to determine the rate of desorption of NO from Pd (111), where it is possible to include anharmonic effects and barrier re-crossing in the dynamics.…”

Section: High-dimensional Quantum Dynamicsmentioning

confidence: 99%

Spiers Memorial Lecture: New directions in molecular scattering

Schatz,

Wodtke,

Yang

2024

Faraday Discuss.

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Section: High-dimensional Quantum Dynamicsmentioning

confidence: 99%

Spiers Memorial Lecture: New directions in molecular scattering

Schatz,

Wodtke,

Yang

2024

Faraday Discuss.

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“…By doing this, NQEs, such as tunneling and ZPE conservation, are included at a reasonable increase of cost (generally 1–2 orders of magnitude compared to QCT). RPMD has been successfully applied to, e.g., gas phase reactions, − hydrogen diffusion on and NO desorption from metal surfaces, , water, − and H atom scattering from graphene . Furthermore, the RPMD approach has also been used to simulate the DC of H 2 on Cu(111) and D 2 O on Ni(111), where it was observed that RPMD can accurately reproduce wave packet QD .…”

mentioning

confidence: 99%

Accurate Reaction Probabilities for Translational Energies on Both Sides of the Barrier of Dissociative Chemisorption on Metal Surfaces

Gerrits,

Jackson,

Bogaerts

2024

J. Phys. Chem. Lett.

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Molecular dynamics simulations are essential for a better understanding of dissociative chemisorption on metal surfaces, which is often the rate-controlling step in heterogeneous and plasma catalysis. The workhorse quasi-classical trajectory approach ubiquitous in molecular dynamics is able to accurately predict reactivity only for high translational and low vibrational energies. In contrast, catalytically relevant conditions generally involve low translational and elevated vibrational energies. Existing quantum dynamics approaches are intractable or approximate as a result of the large number of degrees of freedom present in molecule−metal surface reactions. Here, we extend a ring polymer molecular dynamics approach to fully include, for the first time, the degrees of freedom of a moving metal surface. With this approach, experimental sticking probabilities for the dissociative chemisorption of methane on Pt(111) are reproduced for a large range of translational and vibrational energies by including nuclear quantum effects and employing full-dimensional simulations.

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“…Surface reactions present additional challenges due to the large number of surface DOFs. So far, some applications of the RPMD approach have been reported for surface processes, − but none has been applied to chemical reactions in which bond breaking and bond formation are present.…”

mentioning

confidence: 99%

Ring Polymer Molecular Dynamics Approach to Quantum Dissociative Chemisorption Rates

Zhang

Zuo

Suleimanov

et al. 2023

J. Phys. Chem. Lett.

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A ring polymer molecular dynamics (RPMD) method is proposed for the calculation of the dissociative chemisorption rate coefficient on surfaces. The RPMD rate theory is capable of handling quantum effects such as the zero-point energy and tunneling in dissociative chemisorption, while it relies on classical trajectories for the simulation. Applications to H2 dissociative chemisorption are demonstrated. For the highly activated process on Ag(111), strong deviations from Arrhenius behavior are found at low temperatures and attributed to tunneling. On Pt(111), where the dissociation has a barrierless pathway, the RPMD rate coefficient is found to agree with the experimentally derived thermal sticking coefficient within a factor of 2 over a large temperature range. Significant quantum effects are also found.

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First-principles surface reaction rates by ring polymer molecular dynamics and neural network potential: role of anharmonicity and lattice motion

Abstract: Elementary gas-surface processes are essential steps in heterogeneous catalysis. A predictive understanding of catalytic mechanisms remains challenging due largely to the difficulties of accurately characterizing of the kinetics of such...

Cited by 4 publications

References 91 publications

Spiers Memorial Lecture: New directions in molecular scattering

Spiers Memorial Lecture: New directions in molecular scattering

Accurate Reaction Probabilities for Translational Energies on Both Sides of the Barrier of Dissociative Chemisorption on Metal Surfaces

Ring Polymer Molecular Dynamics Approach to Quantum Dissociative Chemisorption Rates

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