Absence of isotope effects in the photo-induced desorption of CO from saturated Pd(111) at high laser fluence

Muzas, Alberto S.; Jiménez, Alfredo Serrano; Ovčar, Juraj; Lončarić, Ivor; Alducin, M.; Juaristi, J. I.

doi:10.1016/j.chemphys.2022.111518

Cited by 5 publications

(14 citation statements)

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“…The employed (4×2) surface cell containing two equivalent adsorbates of each kind is the minimum cell that permits including out of phase movements of the adsorbates and a reliable description of the interadsorbates interactions, that are expected to be relevant at sufficiently large coverages. 6,19,[22][23][24][25][26] All (T e , T l )-AIMDEF simulations are performed with vasp 27,28 and the AIMDEF module 19,[29][30][31][32][33][34] using the same computational parameters and the same van der Waals exchange-correlation functional by Dion et al 35 that were used in our previous structural study. 4 Electronic friction coefficients are calculated with the local density friction approximation (LDFA).…”

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confidence: 99%

“…The experimental (2O+CO)/Ru(0001) honeycomb surface, in which CO adsorbs atop a Ru atom and the O atoms occupy the second nearest hcp and fcc sites forming a honeycomb arrangement around the CO, is modeled using a periodic slab with five Ru layers and the adlayer (see Figure S1 in SI). The employed (4 × 2) surface cell containing two equivalent adsorbates of each kind is the minimum cell that permits including out of phase movements of the adsorbates and a reliable description of the interadsorbates interactions, that are expected to be relevant at sufficiently large coverages. ,,− All ( T e , T l )-AIMDEF simulations are performed with vasp , and the AIMDEF module ,− using the same computational parameters and the same van der Waals exchange-correlation functional by Dion et al that were used in our previous structural study . Electronic friction coefficients are calculated with the local density friction approximation (LDFA). , …”

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confidence: 99%

“…The corresponding calculated probabilities of 18.25% and 0.5% yield a branching ratio between the two processes in nearly perfect agreement with the experimental values P des (CO)/ P des (CO 2 ) = 35 and 31 . The agreement must be considered as qualitative because of the limited statistics we have for the oxidation process (two oxidation events in 200 trajectories) and our integration time of 4 ps (note that some oxidation and desorption events may occur beyond this interval, as found for CO desorption from Pd(111)), but it relates already the validity of our nonequilibrium two-temperature picture. As shown below, the fact that the XAS features attributed to the oxidation reaction path are also well reproduced makes our simulations all the more reliable.…”

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confidence: 99%

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Why Ultrafast Photoinduced CO Desorption Dominates over Oxidation on Ru(0001)

Tetenoire

Ehlert

Juaristi

et al. 2022

J. Phys. Chem. Lett.

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CO oxidation on Ru(0001) is a long-standing example of a reaction that, being thermally forbidden in ultrahigh vacuum, can be activated by femtosecond laser pulses. In spite of its relevance, the precise dynamics of the photoinduced oxidation process as well as the reasons behind the dominant role of the competing CO photodesorption remain unclear. Here we use ab initio molecular dynamics with electronic friction that account for the highly excited and nonequilibrated system created by the laser to investigate both reactions. Our simulations successfully reproduce the main experimental findings: the existence of photoinduced oxidation and desorption, the large desorption to oxidation branching ratio, and the changes in the O K-edge X-ray absorption spectra attributed to the initial stage of the oxidation process. Now, we are able to monitor in detail the ultrafast CO desorption and CO oxidation occurring in the highly excited system and to disentangle what causes the unexpected inertness to the otherwise energetically favored oxidation.

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Why Ultrafast Photoinduced CO Desorption Dominates over Oxidation on Ru(0001)

Tetenoire

Ehlert

Juaristi

et al. 2022

J. Phys. Chem. Lett.

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“…For applications in simulations of femtosecond laser-induced desorption, some of us have recently used the embedded atom neural network method 20 to create a machine learning potential of CO/Pd(111) that accurately reproduced the ab-initio results of ref 18 at a much lower computational cost. 21,22 Since the ab-initio data for the paradigmatic system of H/Ru(0001) already exist, 17 we have used these data to create a neural network potential. We then use this potential to simulate femtosecond laser-induced desorption with longer integration times, larger cell sizes, more coverages and isotope ratios as well as laser fluences than hitherto possible.…”

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confidence: 99%

“…Note that, if necessary, the methodology can be extended to include phonon temperature, as shown for the CO/Pd(111) system, 21,22 for example.…”

Section: Introductionmentioning

confidence: 99%

Femtosecond laser-induced desorption of hydrogen molecules from Ru(0001): A systematic study based on machine-learned potentials

Lindner

Lončarić

Vrček

et al. 2023

Preprint

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Femtosecond laser-induced dynamics of molecules on metal surfaces can be seamlessly simulated with all nuclear degrees of freedom using ab-initio molecular dynamics with electronic friction (AIMDEF) and stochastic forces which are a function of a time-dependent electronic temperature. This has recently been demonstrated for hot-electron mediated desorption of hydrogen molecules from a Ru(0001) surface covered with H and D atoms [Juaristi et al., Phys. Rev. B 2017, 95, 125439]. Unfortunately, AIMDEF simulations come with a very large computational expense that severely limits statistics and propagation times. To keep ab-initio accuracy and allow for better statistical sampling, we have developed a neural network interatomic potential of hydrogen on the Ru(0001) surface based on data from ab-initio molecular dynamics simulations of recombinative desorption. Using this potential we simulated femtosecond laser-induced recombinative desorption using varying unit cells, coverages, laser fluences, and isotope ratios with reliable statistics. As a result, we can systematically study a wide range of these parameters and follow dynamics over longer times than hitherto possible, demonstrating that our methodology is a promising way to realistically simulate femtosecond laser-induced dynamics of molecules on metals. Moreover, we show that previously used cell sizes and propagation times were too small to obtain converged results.

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Femtosecond Laser-Induced Desorption of Hydrogen Molecules from Ru(0001): A Systematic Study Based on Machine-Learned Potentials

et al. 2023

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Femtosecond laser-induced dynamics of molecules on metal surfaces can be seamlessly simulated with all nuclear degrees of freedom using ab initio molecular dynamics with electronic friction (AIMDEF) and stochastic forces, which are a function of a time-dependent electronic temperature. This has recently been demonstrated for hot-electron-mediated desorption of hydrogen molecules from a Ru(0001) surface covered with H and D atoms [JuaristiJ. I. Juaristi, J. I. 125439Phys. Rev. B201795]. Unfortunately, AIMDEF simulations come with a very large computational expense that severely limits statistics and propagation times. To keep ab initio accuracy and allow for better statistical sampling, we have developed a neural network interatomic potential of hydrogen on the Ru(0001) surface based on data from ab initio molecular dynamics simulations of recombinative desorption. Using this potential, we simulated femtosecond laser-induced recombinative desorption using varying unit cells, coverages, laser fluences, and isotope ratios with reliable statistics. As a result, we can systematically study a wide range of these parameters and follow dynamics over longer times than hitherto possible, demonstrating that our methodology is a promising way to realistically simulate femtosecond laser-induced dynamics of molecules on metals. Moreover, we show that previously used cell sizes and propagation times were too small to obtain converged results.

show abstract

Absence of isotope effects in the photo-induced desorption of CO from saturated Pd(111) at high laser fluence

Cited by 5 publications

References 73 publications

Why Ultrafast Photoinduced CO Desorption Dominates over Oxidation on Ru(0001)

Why Ultrafast Photoinduced CO Desorption Dominates over Oxidation on Ru(0001)

Femtosecond laser-induced desorption of hydrogen molecules from Ru(0001): A systematic study based on machine-learned potentials

Femtosecond Laser-Induced Desorption of Hydrogen Molecules from Ru(0001): A Systematic Study Based on Machine-Learned Potentials

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