Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

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

doi:10.1016/j.susc.2015.03.011

Cited by 12 publications

(4 citation statements)

References 45 publications

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“…An area of research that has received significant attention at XFELs has been surface photochemistry [447][448][449][450][451][452][453][454]. Many chemical reactions take place on surfaces or interfaces, including many important catalytic reactions, but the ability to trigger these reactions for ultrafast experiments has not been straightforward.…”

Section: Surface Photochemistrymentioning

confidence: 99%

Short-wavelength free-electron laser sources and science: a review

et al. 2017

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This review is focused on free-electron lasers (FELs) in the hard to soft x-ray regime. The aim is to provide newcomers to the area with insights into: the basic physics of FELs, the qualities of the radiation they produce, the challenges of transmitting that radiation to end users and the diversity of current scientific applications. Initial consideration is given to FEL theory in order to provide the foundation for discussion of FEL output properties and the technical challenges of short-wavelength FELs. This is followed by an overview of existing x-ray FEL facilities, future facilities and FEL frontiers. To provide a context for information in the above sections, a detailed comparison of the photon pulse characteristics of FEL sources with those of other sources of high brightness x-rays is made. A brief summary of FEL beamline design and photon diagnostics then precedes an overview of FEL scientific applications. Recent highlights are covered in sections on structural biology, atomic and molecular physics, photochemistry, non-linear spectroscopy, shock physics, solid density plasmas. A short industrial perspective is also included to emphasise potential in this area.

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Section: Surface Photochemistrymentioning

confidence: 99%

Short-wavelength free-electron laser sources and science: a review

et al. 2017

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“…Recently, CO desorption from CO=Ru was studied on picosecond timescales, and a weakly adsorbed precursor state [11,22] was directly identified and its evolution described [14]. In this Letter, we focus on the ultrafast dynamics occurring in the CO within the very first picosecond following optical laser excitation of the Ru.…”

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confidence: 99%

Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy

Diesen¹,

Wang²,

Schreck³

et al. 2021

Phys. Rev. Lett.

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We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO=Ruð0001Þ after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ∼100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes.

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“…In systems where the binding energies of fully saturated gas-phase species are small, such as metals, desorption barriers are not often considered because they are rarely rate-determining. However, in materials where the binding energies of these species is significant (for example, RuO 2 (110) binds fully coordinated molecules such as formaldehyde, water and methanol with enthalpies of ∼1.1, 1.2, and 1.3 eV, respectively), desorption barriers have been measured experimentally and have the potential to drastically change the kinetic picture . While it is not trivial to determine these desorption free-energy barriers from first-principles, Campbell et al have compiled an extensive list of desorption activation energies and prefactors for a range of molecules and surfaces .…”

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confidence: 99%

A Theoretical Study of Methanol Oxidation on RuO₂(110): Bridging the Pressure Gap

2017

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Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due to a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. We believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.

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Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

Cited by 12 publications

References 45 publications

Short-wavelength free-electron laser sources and science: a review

Short-wavelength free-electron laser sources and science: a review

Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy

A Theoretical Study of Methanol Oxidation on RuO₂(110): Bridging the Pressure Gap

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Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state

Cited by 12 publications

References 45 publications

Short-wavelength free-electron laser sources and science: a review

Short-wavelength free-electron laser sources and science: a review

Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy

A Theoretical Study of Methanol Oxidation on RuO2(110): Bridging the Pressure Gap

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Product

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A Theoretical Study of Methanol Oxidation on RuO₂(110): Bridging the Pressure Gap