7D Quantum Dynamics of H2 Scattering from Cu(111): The Accuracy of the Phonon Sudden Approximationy
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Matteo Bonfanti
Abstract
The correct prediction of elementary processes occurring when H2 scatters from a metal surface is one of the main challenges of surface science. In the field, the scattering of H2 from Cu(111) has been considered a prototype system for activated dissociative chemisorption. Experimental and theoretical work suggested that a proper description of some scattering experiments on this system might require going beyond the static surface approximation, to consider how the motion of the Cu atoms affects the scattering event. Previous work suggested that important effects of phonons on the dynamics can be incorporated in the Potential Energy Surface (PES) by including four degrees of freedom, that have approximately additive couplings with the hydrogen molecule: the 3 dimensional motion of the nearest 1st layer copper atom and the displacement of the nearest 2nd layer copper atom along the direction perpendicular to the surface [3]. In the present work, we extend the 6D dynamical model by including the perpendicular motion of the 2nd layer surface atom and we study this novel dynamical model with two techniques: an approximate method based on the Phonon Sudden Approximation (PSA) and an exact description using 7D wavepacket quantum dynamics. We consider how the inclusion and the excitation of the lattice degree of freedom affect some relevant processes: dissociative chemisorption, vibrational excitation of H2 and state-to-state scattering probabilities fully resolved with respect to the vibrational states of the surface. We show that the PSA works in an excellent way for the system, thereby suggesting that this might be a viable way to study higher dimensional quantum models, incorporating four surface degrees of freedom that appear to be most relevant for H2 scattering.
© 2013 by Walter de Gruyter Berlin Boston
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- Personal Perspective
- A Comment on Henry Eyring
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- Historical Paper
- On Simple Gas Reactions
- Feature Article
- Probing Quantum Dynamics of Elementary Chemical Reactions via Accurate Potential Energy Surfaces
- Elementary Gas Phase Reactions
- Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO
- Simultaneous Measurement of Reactive and Inelastic Scattering: Differential Cross Section of the H + HD → HD(v′, j′) + H Reaction
- The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst
- A Theoretical Study of the X-Abstraction Reactions (X = H, Br, or I) from CH2IBr by OH Radicals: Implications for Atmospheric Chemistry
- Models for Intrinsic Non-RRKM Dynamics. Decomposition of the SN2 Intermediate Cl––CH3Br
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- Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison
- 7D Quantum Dynamics of H2 Scattering from Cu(111): The Accuracy of the Phonon Sudden Approximationy
- Exploring Pathways of Photoaddition Reactions by Artificial Force Induced Reaction Method: A Case Study on the Paternò–Büchi Reaction
- Kinetic Prefactors of Reactions on Solid Surfaces
- Electron-Transfer-Induced Dissociation of H2 on Gold Nanoparticles: Excited-State Potential Energy Surfaces via Embedded Correlated Wavefunction Theory
- 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
- Initial Sticking Coefficient of H2 on the Pd–Cu(111) Surface Alloy at very Low Coverages
- Catalyzed Surface-Aligned Reaction, H(ad) + H2(ad) = H2(g) + H(ad) on Coinage Metals
- Nitrogen Scattering at Ru(0001) Surfaces
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- Embedded Cluster Models for Reactivity of the Hydrated Electron
- Novel Experimenta Methods
- Stark Deceleration of NO Radicals
- A Forty-Segment Molecular Synchrotron
Articles in the same Issue
- Masthead
- Masthead
- Editorial
- Milestones in Physical Chemistry (I) – A Special Issue Honoring the Seminal Work of Henry Eyring and Michael Polanyi
- International Collaborations are nothing new... and sometimes they are simply amazing
- Personal Perspective
- A Comment on Henry Eyring
- Comment
- Michael Polanyi, the Scientist
- Historical Paper
- On Simple Gas Reactions
- Feature Article
- Probing Quantum Dynamics of Elementary Chemical Reactions via Accurate Potential Energy Surfaces
- Elementary Gas Phase Reactions
- Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO
- Simultaneous Measurement of Reactive and Inelastic Scattering: Differential Cross Section of the H + HD → HD(v′, j′) + H Reaction
- The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst
- A Theoretical Study of the X-Abstraction Reactions (X = H, Br, or I) from CH2IBr by OH Radicals: Implications for Atmospheric Chemistry
- Models for Intrinsic Non-RRKM Dynamics. Decomposition of the SN2 Intermediate Cl––CH3Br
- Chemical Reactions at Surfaces
- Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison
- 7D Quantum Dynamics of H2 Scattering from Cu(111): The Accuracy of the Phonon Sudden Approximationy
- Exploring Pathways of Photoaddition Reactions by Artificial Force Induced Reaction Method: A Case Study on the Paternò–Büchi Reaction
- Kinetic Prefactors of Reactions on Solid Surfaces
- Electron-Transfer-Induced Dissociation of H2 on Gold Nanoparticles: Excited-State Potential Energy Surfaces via Embedded Correlated Wavefunction Theory
- 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
- Initial Sticking Coefficient of H2 on the Pd–Cu(111) Surface Alloy at very Low Coverages
- Catalyzed Surface-Aligned Reaction, H(ad) + H2(ad) = H2(g) + H(ad) on Coinage Metals
- Nitrogen Scattering at Ru(0001) Surfaces
- Ready, Set and no Action: A Static Perspective on Potential Energy Surfaces commonly used in Gas-Surface Dynamics
- Reactions in Clusters
- Potential Energy Surfaces and Rates of Spin Transitions
- A Full-Dimensional Neural Network Potential-Energy Surface for Water Clusters up to the Hexamer
- Embedded Cluster Models for Reactivity of the Hydrated Electron
- Novel Experimenta Methods
- Stark Deceleration of NO Radicals
- A Forty-Segment Molecular Synchrotron
