Electronically Nonadiabatic Processes in the Interaction of H with a Au Surface Revealed Using MIM Junctions: The Temperature Dependence

Schindler, Beate; Diesing, Detlef; Hasselbrink, Eckart

doi:10.1021/jp4009459

Cited by 22 publications

(32 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Importantly, this is consistent with the fact that chemicurrent intensities measured during the chemisorption of atoms and molecules scale with the adsorption energy [13][14][15]. Chemicurrents have also been observed during the associative desorption of H 2 on metal surfaces [42,43]. Our finding shows that in these experiments a large amount of e-h pair excitation may take place during the motion of the H atoms on the surface prior to recombination.…”

supporting

confidence: 88%

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

et al. 2014

View full text Add to dashboard Cite

We study the dynamics of transient hot H atoms on Pd(100) that originated from dissociative adsorption of H 2 . The methodology developed here, denoted AIMDEF, consists of ab initio molecular dynamics simulations that include a friction force to account for the energy transfer to the electronic system. We find that the excitation of electron-hole pairs is the main channel for energy dissipation, which happens at a rate that is five times faster than energy transfer into Pd lattice motion. Our results show that electronic excitations may constitute the dominant dissipation channel in the relaxation of hot atoms on surfaces. DOI: 10.1103/PhysRevLett.112.103203 PACS numbers: 68.43.-h, 34.35.+a, 34.50.Bw, 82.20.Gk Electron-hole (e-h) pair excitations are an unquestioned efficient energy drain in the interaction of fast atoms with solids and surfaces [1][2][3][4]. In contrast, the relevance of this dissipation channel in gas-surface interactions that involve energies up to a few eV is not so clear. It depends not only on the specific system, but also on the elementary process considered, as shown by different studies on scattering [5][6][7][8][9][10][11][12] and adsorption [6,[13][14][15][16][17][18][19][20][21][22][23][24][25][26] of atoms and molecules on surfaces. Low-energy e-h pair excitations have been detected as chemicurrents on Schottky diode devices during the chemisorption of atomic and molecular species on metals [13][14][15]. The correlation found between chemicurrent intensities and adsorption energies is a strong indication that a large fraction of the energy dissipated in both the dissociative and nondissociative adsorption processes is used to excite e-h pairs. However, this strongly contrasts with examples showing that the dissociative adsorption is reasonably well described within the electronically adiabatic approach, which neglects the coupling between electronic excitations and the nuclear motion [6,[18][19][20]23,25], and that the effect of electronic energy dissipation seems negligible [21,24,26]. Therefore, a question that is raised here is at what stage of the dissociative adsorption process e-h pair excitations do become relevant.In a typical adsorption event, the incoming gas species gain additional kinetic energy when entering the attractive adsorption well. In the particular case of dissociative adsorption, this energy gain can lead to the formation of so-called "hot" atoms or fragments, with energies much larger than the corresponding thermal energies of the substrate atoms. The formed hot species will then propagate along the surface until they dissipate the excess kinetic energy and finally accommodate at a stable adsorption position. This stage of the dissociative adsorption process, where the relevance of e-h pair excitations has been traditionally neglected, is the focus of the present work.In this Letter we show that while e-h pair excitation may not be relevant on the molecule-bond-breaking time scale, it is an efficient dissipative channel in the subsequent relaxation of the...

show abstract

supporting

confidence: 88%

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

et al. 2014

View full text Add to dashboard Cite

show abstract

“…A possible reason might be that the calculations neglect nonadiabatic effects, which have been observed in surface scattering experiments for the same system (14)(15)(16). Work by Hasselbrink and coworkers (147)(148)(149) has detected the possible presence of nonadiabatic effects in the recombination of H atoms on gold surfaces, which implies their presence in the reverse dissociative chemisorption reaction. Further quantum state-resolved reactivity studies on the dissociative chemisorption in these two systems might yield experimental evidence of electronically nonadiabatic effects.…”

Section: Discussionmentioning

confidence: 95%

Quantum State–Resolved Studies of Chemisorption Reactions

Chadwick

Beck

2017

Annu. Rev. Phys. Chem.

View full text Add to dashboard Cite

Chemical reactions at the gas-surface interface are ubiquitous in the chemical industry as well as in nature. Investigating these processes at a microscopic, quantum state-resolved level helps develop a predictive understanding of this important class of reactions. In this review, we present an overview of the field of quantum state-resolved gas-surface reactivity measurements that explore the role of the initial quantum state on the dissociative chemisorption of a gas-phase reactant incident on a solid surface. Using molecular beams and either quantum state-specific reactant preparation or product detection by laser excitation, these studies have observed mode specificity and bond selectivity as well as steric effects in chemisorption reactions, highlighting the nonstatistical and complex nature of gas-surface reaction dynamics.

show abstract

“…A similar feature is also observed for Au at lower T S , but it is always only a superposition to the signal assigned to the LH recombination reaction. In a recent paper we identified this feature to arise from a shift of the Fermi level due to the charge transfer connected with adsorption of H to the surface resulting in a capacitor charging/discharging current when the H atom beam is flagged on and off [49].…”

Section: Discussionmentioning

confidence: 99%

Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison

Schindler

Diesing

Hasselbrink

2013

Zeitschrift für Physikalische Chemie

Self Cite

View full text Add to dashboard Cite

The creation of electronic excitations during the reaction of atomic hydrogen on and with coinage and noble metals has been studied using metal-insulator-metal heterostructures. A characteristic current trace is observed when the outer metal surface of the structure is exposed to a 20 s pulse of H atoms. Comparison to the chemical kinetics allows to disentangle the contributions from the different chemical processes to this current. In the case of the coinage metals studied the observation is interpreted to suggest that predominantly electrons excited in connection with the hydrogen recombination reaction are the source of the current. For Pt such phenomenon is not observed. This difference allows insights into the role of the transition state for the non-adiabaticity in this simple chemical reaction.

show abstract

Electronically Nonadiabatic Processes in the Interaction of H with a Au Surface Revealed Using MIM Junctions: The Temperature Dependence

Cited by 22 publications

References 30 publications

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

Quantum State–Resolved Studies of Chemisorption Reactions

Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison

Contact Info

Product

Resources

About