Selective Ultrafast Probing of Transient Hot Chemisorbed and Precursor States of CO on Ru(0001)

Beye, Martin; Anniyev, Toyli; Coffee, Ryan; Dell’Angela, Martina; Föhlisch, Alexander; Gladh, Jörgen; Katayama, Tetsuo; Kaya, Sarp; Krupin, O.; Møgelhøj, Andreas; Nilsson, Anders; Nordlund, Dennis; Nørskov, Jens K.; Öberg, Henrik; Ogasawara, Hirohito; Pettersson, Lars G. M.; Schlotter, W. F.; Sellberg, Jonas A.; Sorgenfrei, F.; Turner, Joshua J.; Wolf, Martin; Würth, W.; Öström, Henrik

doi:10.1103/physrevlett.110.186101

Cited by 56 publications

(56 citation statements)

References 26 publications

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“…[50][51][52][53] From the experiments of femtosecond laser-induced oxidation of CO on Ru(100), the CO oxidation driven by an electronic excitation (fast response) and the CO desorption coupled with phonons (slow response) were distinguished. 50 Also, the two-step mechanism of the CO desorption on Ru(0001) has been demonstrated.…”

Section: Discussionmentioning

confidence: 99%

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Phonocatalysis. An ab initio simulation experiment

Kim

Kaviany

2016

AIP Advances

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Using simulations, we postulate and show that heterocatalysis on large-bandgap semiconductors can be controlled by substrate phonons, i.e., phonocatalysis. With ab initio calculations, including molecular dynamic simulations, the chemisorbed dissociation of XeF6 on h-BN surface leads to formation of XeF4 and two surface F/h-BN bonds. The reaction pathway and energies are evaluated, and the sorption and reaction emitted/absorbed phonons are identified through spectral analysis of the surface atomic motion. Due to large bandgap, the atomic vibration (phonon) energy transfer channels dominate and among them is the match between the F/h-BN covalent bond stretching and the optical phonons. We show that the chemisorbed dissociation (the pathway activation ascent) requires absorption of large-energy optical phonons. Then using progressively heavier isotopes of B and N atoms, we show that limiting these high-energy optical phonons inhibits the chemisorbed dissociation, i.e., controllable phonocatalysis.

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Section: Discussionmentioning

confidence: 99%

“…50 Also, the two-step mechanism of the CO desorption on Ru(0001) has been demonstrated. 51,52 The state-of-the-art attosecond technology has delved into the dissociative dynamics of N + 2 .…”

Section: Discussionmentioning

confidence: 99%

Phonocatalysis. An ab initio simulation experiment

Kim

Kaviany

2016

AIP Advances

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“…Aside from diffractive imaging, considerable attention has also been paid to the potential of XFELs with respect to spectroscopic applications [9,10]. The capability of XFELs to provide ultrashort pulses has enabled novel time-resolved spectroscopic experiments [11][12][13][14]. The work presented here is connected to the ultrahigh intensity of XFELs that has rendered a new regime in nonlinear x-ray spectroscopy accessible [15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

et al. 2018

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With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

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“…For example, this system was the subject of experimental investigations on FL induced desorption [6][7][8], FL induced formation of "hot" adsorbates [8,9], adsorbate diffusion on the surface [9], recombinative desorption of CO from C/O coadsorbates [10], as well as FL induced oxidation (to CO 2 ) and desorption (of CO) of CO/O coadsorbates [11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion

et al. 2016

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A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 × 2):CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.

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Selective Ultrafast Probing of Transient Hot Chemisorbed and Precursor States of CO on Ru(0001)

Cited by 56 publications

References 26 publications

Phonocatalysis. An ab initio simulation experiment

Phonocatalysis. An ab initio simulation experiment

Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion

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