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| 2. |
- Fomalont, E. B., et al.
(författare)
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THE 2014 ALMA LONG BASELINE CAMPAIGN: AN OVERVIEW
- 2015
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Ingår i: Astrophysical Journal Letters. - : American Astronomical Society. - 2041-8213 .- 2041-8205. ; 808:1
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Tidskriftsartikel (refereegranskat)abstract
- A major goal of the Atacama Large Millimeter/submillimeter Array (ALMA) is to make accurate images with resolutions of tens of milliarcseconds, which at submillimeter (submm) wavelengths requires baselines up to similar to 15 km. To develop and test this capability, a Long Baseline Campaign (LBC) was carried out from 2014 September to late November, culminating in end-to-end observations, calibrations, and imaging of selected Science Verification (SV) targets. This paper presents an overview of the campaign and its main results, including an investigation of the short-term coherence properties and systematic phase errors over the long baselines at the ALMA site, a summary of the SV targets and observations, and recommendations for science observing strategies at long baselines. Deep ALMA images of the quasar 3C 138 at 97 and 241 GHz are also compared to VLA 43 GHz results, demonstrating an agreement at a level of a few percent. As a result of the extensive program of LBC testing, the highly successful SV imaging at long baselines achieved angular resolutions as fine as 19 mas at similar to 350 GHz. Observing with ALMA on baselines of up to 15 km is now possible, and opens up new parameter space for submm astronomy.
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| 3. |
- Xin, H., et al.
(författare)
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Strong Influence of Coadsorbate Interaction on CO Desorption Dynamics on Ru(0001) Probed by Ultrafast X-Ray Spectroscopy and Ab Initio Simulations
- 2015
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:15
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Tidskriftsartikel (refereegranskat)abstract
- We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.
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| 4. |
- Öberg, Henrik, et al.
(författare)
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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
- 2015
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 640, s. 80-88
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Tidskriftsartikel (refereegranskat)abstract
- We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of similar to 2000K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (similar to 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate.
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| 5. |
- Östrom, Henrik, et al.
(författare)
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Probing the transition state region in catalytic CO oxidation on Ru
- 2015
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 347:6225, s. 978-982
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Tidskriftsartikel (refereegranskat)abstract
- Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
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| 6. |
- Dell'Angela, M., et al.
(författare)
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Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer
- 2015
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Ingår i: Structural Dynamics. - : AIP Publishing. - 2329-7778. ; 2:2
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Tidskriftsartikel (refereegranskat)abstract
- Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse.
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| 7. |
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| 8. |
- LaRue, Jerry, et al.
(författare)
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Real-Time Elucidation of Catalytic Pathways in CO Hydrogenation on Ru
- 2017
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Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185 .- 1948-7185. ; 8:16, s. 3820-3825
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Tidskriftsartikel (refereegranskat)abstract
- The direct elucidation of the reaction pathways in heterogeneous catalysis has been challenging due to the short-lived nature of reaction intermediates. Here, we directly measured on ultrafast time scales the initial hydrogenation steps of adsorbed CO on a Ru catalyst surface, which is known as the bottleneck reaction in syngas and CO2 reforming processes. We initiated the hydrogenation of CO with an ultrafast laser temperature jump and probed transient changes in the electronic structure using real-time X-ray spectroscopy. In combination with theoretical simulations, we verified the formation of CHO during CO hydrogenation.
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| 9. |
- Nilsson, Anders, et al.
(författare)
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Catalysis in real time using X-ray lasers
- 2017
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 675, s. 145-173
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Tidskriftsartikel (refereegranskat)abstract
- We describe how the unique temporal and spectral characteristics of X-ray free-electron lasers (XFEL) can be utilized to follow chemical transformations in heterogeneous catalysis in real time. We highlight the systematic study of CO oxidation on Ru(0001), which we initiate either using a femtosecond pulse from an optical laser or by activating only the oxygen atoms using a THz pulse. We find that CO is promoted into an entropy-controlled precursor state prior to desorbing when the surface is heated in the absence of oxygen, whereas in the presence of oxygen, CO desorbs directly into the gas phase. We monitor the activation of atomic oxygen explicitly by the reduced split between bonding and antibonding orbitals as the oxygen comes out of the strongly bound hollow position. Applying these novel XFEL techniques to the full oxidation reaction resulted in the surprising observation of a significant fraction of the reactants at the transition state through the electronic signature of the new bond formation.
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| 10. |
- Eilert, André, et al.
(författare)
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Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction
- 2017
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Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185 .- 1948-7185. ; 8:1, s. 285-290
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Tidskriftsartikel (refereegranskat)abstract
- Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stable under the strongly reducing conditions found in CO2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.
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