Role of Electron-Hole Pair Excitations in the Dissociative Adsorption of Diatomic Molecules on Metal Surfaces

Juaristi, J. I.; Alducin, M.; Muiño, R. Dı́ez; Busnengo, H. F.; Salin, A.

doi:10.1103/physrevlett.100.116102

Cited by 243 publications

(312 citation statements)

References 27 publications

Supporting

Mentioning

305

Contrasting

Order By: Relevance

“…This suggests that the PES used accurately describes the anisotropy of the molecule-surface interaction, and it raises the question why the combination of the semiempirical PES and model used here reproduces data on rotationally inelastic scattering, but not on vibrationally inelastic scattering. Furthermore, the SRP-DFT PES we used accurately describes (21) those experiments on reactive scattering of H 2 from Cu (111) for which the BOSS model is expected to hold, based on previous theoretical research (15)(16)(17)(18)21) and experiments (19)(20)(21). The fact that this PES yields accurate results concerning how vibrational preexcitation of H 2 promotes reaction suggests (7) that the features of the PES responsible for promoting vibrational excitation [large curvature of the reaction path in front of a late barrier (7)] should also be accurately described, at least at the reactive sites.…”

Section: Discussionmentioning

confidence: 99%

“…Vibrationally inelastic scattering may also be promoted by energy exchange with electron-hole (e-h) pairs (3,13,14). The H 2 þ Cu system is a benchmark system for investigating the effects of e-h pair excitation (15,16) and energy transfer to phonons (12,17) on reaction of molecules with metal surfaces. Theoretical studies on e-h pair excitation suggest the effects to be small (15,16), in line with research on H 2 þ Ptð111Þ (18).…”

mentioning

confidence: 99%

“…The H 2 þ Cu system is a benchmark system for investigating the effects of e-h pair excitation (15,16) and energy transfer to phonons (12,17) on reaction of molecules with metal surfaces. Theoretical studies on e-h pair excitation suggest the effects to be small (15,16), in line with research on H 2 þ Ptð111Þ (18). Also, specific features have been identified in PESs for H 2 þ Cu that promote vibrationally inelastic scattering in an electronically adiabatic mechanism (6)(7)(8).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

Kroes

Dı́az

Pijper

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

109

View full text Add to dashboard Cite

The accuracy of dynamical models for reactive scattering of molecular hydrogen, H 2 , from metal surfaces is relevant to the validation of first principles electronic structure methods for molecules interacting with metal surfaces. The ability to validate such methods is important to progress in modeling heterogeneous catalysis. Here, we study vibrational excitation of H 2 on Cu(111) using the Born-Oppenheimer static surface model. The potential energy surface (PES) used was validated previously by calculations that reproduced experimental data on reaction and rotationally inelastic scattering in this system with chemical accuracy to within errors ≤ 1 kcal∕mol ≈ 4.2 kJ∕mol [Díaz C, et al. (2009) Science 326:832-834]. Using the same PES and model, our dynamics calculations underestimate the contribution of vibrational excitation to previously measured time-of-flight spectra of H 2 scattered from Cu(111) by a factor 3. Given the accuracy of the PES for the experiments for which the Born-Oppenheimer static surface model is expected to hold, we argue that modeling the effect of the surface degrees of freedom will be necessary to describe vibrational excitation with similar high accuracy.Born-Oppenheimer approximation | dissociative chemisorption | molecule-surface scattering R eactions of molecules with metal surfaces are of tremendous importance, as the production of most man-made chemicals involves heterogeneous catalysis by a metal surface. One of the achievements recognized by the 2007 Nobel Prize in Chemistry, awarded to G. Ertl, was the detailed description of the sequence of elementary molecule-surface reactions by which ammonia is produced (1). In such reaction sequences, the dissociative chemisorption of molecules often plays a prominent role.In the present state of the art, theoretical calculations can reproduce overall rates of heterogeneously catalyzed reactions like ammonia production to within an order of magnitude (2). Achieving greater precision has been hampered by the lack of accuracy inherent in the density functional theory (DFT) used to calculate the interactions of molecules with metal surfaces.Because dissociative chemisorption involves stretching bonds until they rupture, reactivity of molecules on surfaces is closely related to transfer of energy to and from the vibrational degrees of freedom (3). Thus vibrationally inelastic scattering can be a sensitive probe of the barrier region of the potential energy surface (PES), and experiments (4, 5) and theory (6, 7) suggest that this process is governed by the same region of the PES as dissociative chemisorption: The picture of vibrational excitation occurring in competition with dissociative chemisorption is that it results from a stretching of the molecule as it approaches the transition state (4, 5). In principle, experiments on this competition may reveal much interesting information. For instance, comparison of data on vibrationally inelastic scattering and reaction on a surface has been suggested to provide information on whether these pro...

show abstract

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

Kroes

Dı́az

Pijper

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

109

View full text Add to dashboard Cite

show abstract

“…It employs Langevin molecular dynamics (MD) to obtain H/D-atom translational energy loss distributions including the effect of electron-hole pair (EHP) excitation; this part of the theory builds on previous work employing a local density friction approximation (LDFA) (17). LDFA combined with ab initio molecular dynamics (AIMD) has also been previously applied to study the associative desorption of diatomics at metal surfaces (18)(19)(20). Here, we extend the LDFA theory to describe the energy spectrum of the excited EHPs produced by the MD trajectories by implementing a forced oscillator model (FOM) (21)(22)(23).…”

mentioning

confidence: 99%

Unified description of H-atom–induced chemicurrents and inelastic scattering

Kandratsenka

Jiang

Dorenkamp

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

The Born-Oppenheimer approximation (BOA) provides the foundation for virtually all computational studies of chemical binding and reactivity, and it is the justification for the widely used "balls and springs" picture of molecules. The BOA assumes that nuclei effectively stand still on the timescale of electronic motion, due to their large masses relative to electrons. This implies electrons never change their energy quantum state. When molecules react, atoms must move, meaning that electrons may become excited in violation of the BOA. Such electronic excitation is clearly seen for: (i) Schottky diodes where H adsorption at Ag surfaces produces electrical "chemicurrent;" (ii) Au-based metal-insulator-metal (MIM) devices, where chemicurrents arise from H-H surface recombination; and (iii) Inelastic energy transfer, where H collisions with Au surfaces show H-atom translation excites the metal's electrons. As part of this work, we report isotopically selective hydrogen/deuterium (H/D) translational inelasticity measurements in collisions with Ag and Au. Together, these experiments provide an opportunity to test new theories that simultaneously describe both nuclear and electronic motion, a standing challenge to the field. Here, we show results of a recently developed first-principles theory that quantitatively explains both inelastic scattering experiments that probe nuclear motion and chemicurrent experiments that probe electronic excitation. The theory explains the magnitude of chemicurrents on Ag Schottky diodes and resolves an apparent paradox--chemicurrents exhibit a much larger isotope effect than does H/D inelastic scattering. It also explains why, unlike Ag-based Schottky diodes, Au-based MIM devices are insensitive to H adsorption.M ost theoretical studies of atoms and molecules interacting with metal surfaces are based on the Born-Oppenheimer approximation (BOA) (1). However, a growing number of examples have been found where electronic and nuclear degrees of freedom are strongly coupled in violation of the BOA (2-6). H-atom interactions at metals offer a remarkable opportunity to test non-BOA theories against experiment, since H-adsorptioninduced chemicurrent experiments (7-14) offer a direct measure of electronic excitation and H-atom inelastic scattering experiments (15) directly probe nuclear motion. In chemicurrent experiments, exothermic H interactions like adsorption and recombination produce hot electrons that pass over a potential barrier to be collected. Hence, the magnitude of the chemicurrent is dependent on both the reaction-induced production of hot electrons and the likelihood of transmission over the barrier. To reduce uncertainties associated with barrier transmission, the ratio of hydrogen-and deuterium-induced chemicurrent is often measured--H-induced chemicurrents are typically two to five times larger than those from D atoms (7,(11)(12)(13). H-atom surface scattering experiments yield H-atom translational energy loss distributions. The importance of H-atom translation to electronic exc...

show abstract

“…In past decades, considerable research has been focused on investigating the friction behaviors at the microor nano-scales based on theory and simulations. The concept of friction has been extended in a number of associated areas, such as using surface roughness [3,4], phonon and electron excitation [5][6][7], and dislocation interaction theories [8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Nanoscale Friction Behavior of the Ni-Film/Substrate System Under Scratching Using MD Simulation

Liu

Wei

2012

Tribol Lett

View full text Add to dashboard Cite

The friction behavior of the nanoscratching process is investigated using molecular dynamic simulations by considering a sphere indenter sliding against a nickel nanofilm structure. In the film/substrate system, the interface-dominated friction process is studied during the nanoscratch process. The results indicate that the interface accommodates deformation during the scratch by absorbing plastic deformation (such as stacking faults and partial dislocations) and by allowing locally interface slip. The observed local material shuffling beneath the tip that was strongly affected by the interface and friction mechanisms, including material ploughing along the track, filling in of the track, and piling up of the chip in front of the tip, are discussed. The combination effects of both scratching depths and film thicknesses were also investigated.

show abstract

Role of Electron-Hole Pair Excitations in the Dissociative Adsorption of Diatomic Molecules on Metal Surfaces

Cited by 243 publications

References 27 publications

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

Apparent failure of the Born–Oppenheimer static surface model for vibrational excitation of molecular hydrogen on copper

Unified description of H-atom–induced chemicurrents and inelastic scattering

Nanoscale Friction Behavior of the Ni-Film/Substrate System Under Scratching Using MD Simulation

Contact Info

Product

Resources

About