| 1. |
- Östrom, Henrik, et al.
(author)
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Probing the transition state region in catalytic CO oxidation on Ru
- 2015
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In: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 347:6225, s. 978-982
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Journal article (peer-reviewed)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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| 2. |
- Stolper, E.M., et al.
(author)
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The petrochemistry of Jake_M : A martian mugearite
- 2013
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In: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 341:6153
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Journal article (peer-reviewed)abstract
- “Jake_M,” the first rock analyzed by the Alpha Particle X-ray Spectrometer instrument on the Curiosity rover, differs substantially in chemical composition from other known martian igneous rocks: It is alkaline (>15% normative nepheline) and relatively fractionated. Jake_M is compositionally similar to terrestrial mugearites, a rock type typically found at ocean islands and continental rifts. By analogy with these comparable terrestrial rocks, Jake_M could have been produced by extensive fractional crystallization of a primary alkaline or transitional magma at elevated pressure, with or without elevated water contents. The discovery of Jake_M suggests that alkaline magmas may be more abundant on Mars than on Earth and that Curiosity could encounter even more fractionated alkaline rocks (for example, phonolites and trachytes).
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| 3. |
- Vaughan, A., et al.
(author)
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Regolith of the Crater Floor Units, Jezero Crater, Mars : Textures, Composition, and Implications for Provenance
- 2023
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In: Journal of Geophysical Research - Planets. - : John Wiley and Sons Inc. - 2169-9097 .- 2169-9100. ; 128:3
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Journal article (peer-reviewed)abstract
- A multi-instrument study of the regolith of Jezero crater floor units by the Perseverance rover has identified three types of regolith: fine-grained, coarse-grained, and mixed-type. Mastcam-Z, Wide Angle Topographic Sensor for Operations and eNgineering, and SuperCam Remote Micro Imager were used to characterize the regolith texture, particle size, and roundedness where possible. Mastcam-Z multispectral and SuperCam laser-induced breakdown spectroscopy data were used to constrain the composition of the regolith types. Fine-grained regolith is found surrounding bedrock and boulders, comprising bedforms, and accumulating on top of rocks in erosional depressions. Spectral and chemical data show it is compositionally consistent with pyroxene and a ferric-oxide phase. Coarse-grained regolith consists of 1–2 mm well-sorted gray grains that are found concentrated around the base of boulders and bedrock, and armoring bedforms. Its chemistry and spectra indicate it is olivine-bearing, and its spatial distribution and roundedness indicate it has been transported, likely by saltation-induced creep. Coarse grains share similarities with the olivine grains observed in the Séítah formation bedrock, making that unit a possible source for these grains. Mixed-type regolith contains fine- and coarse-grained regolith components and larger rock fragments. The rock fragments are texturally and spectrally similar to bedrock within the Máaz and Séítah formations, indicating origins by erosion from those units, although they could also be a lag deposit from erosion of an overlying unit. The fine- and coarse-grained types are compared to their counterparts at other landing sites to inform global, regional, and local inputs to regolith formation within Jezero crater. The regolith characterization presented here informs the regolith sampling efforts underway by Perseverance. © 2023. The Authors.
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| 4. |
- Kjellsson, Ludvig, et al.
(author)
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Resonant Inelastic X-Ray Scattering Reveals Hidden Local Transitions of the Aqueous OH Radical
- 2020
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In: Physical Review Letters. - : AMER PHYSICAL SOC. - 0031-9007 .- 1079-7114. ; 124:23
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Journal article (peer-reviewed)abstract
- Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultra-fast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH(aq). Impulsive ionization of pure liquid water produced a short-lived population of OH(aq), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions-thus providing a means to investigate the evolving electronic structure and reactivity of the hydroxyl radical in aqueous and heterogeneous environments. First-principles calculations provide interpretation of the main spectral features.
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| 5. |
- Loh, Z-H, et al.
(author)
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Observation of the fastest chemical processes in the radiolysis of water
- 2020
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In: Science. - : AMER ASSOC ADVANCEMENT SCIENCE. - 0036-8075 .- 1095-9203. ; 367:6474, s. 179-182
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Journal article (peer-reviewed)abstract
- Elementary processes associated with ionization of liquid water provide a framework for understanding radiation-matter interactions in chemistry and biology. Although numerous studies have been conducted on the dynamics of the hydrated electron, its partner arising from ionization of liquid water, H2O+, remains elusive. We used tunable femtosecond soft x-ray pulses from an x-ray free electron laser to reveal the dynamics of the valence hole created by strong-field ionization and to track the primary proton transfer reaction giving rise to the formation of OH. The isolated resonance associated with the valence hole (H2O+/OH) enabled straightforward detection. Molecular dynamics simulations revealed that the x-ray spectra are sensitive to structural dynamics at the ionization site. We found signatures of hydrated-electron dynamics in the x-ray spectrum.
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| 6. |
- Xin, H., et al.
(author)
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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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In: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:15
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Journal article (peer-reviewed)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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| 7. |
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| 8. |
- LaRue, Jerry, et al.
(author)
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Real-Time Elucidation of Catalytic Pathways in CO Hydrogenation on Ru
- 2017
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In: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 8:16, s. 3820-3825
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Journal article (peer-reviewed)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. |
- Shen, L., et al.
(author)
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Decoupling spin-orbital correlations in a layered manganite amidst ultrafast hybridized charge-transfer band excitation
- 2020
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In: Physical Review B. - 2469-9950. ; 101:20
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Journal article (peer-reviewed)abstract
- In the mixed-valence manganites, a near-infrared laser typically melts the orbital and spin order simultaneously, corresponding to the photoinduced d1d0→d0d1 excitations in the Mott-Hubbard bands of manganese. Here, we use ultrafast methods-both femtosecond resonant X-ray diffraction and optical reflectivity-to demonstrate that the orbital response in the layered manganite Nd1-xSr1+xMnO4(x=2/3) does not follow this scheme. At the photoexcitation saturation fluence, the orbital order is only diminished by a few percent in the transient state. Instead of the typical d1d0→d0d1 transition, a near-infrared pump in this compound promotes a fundamentally distinct mechanism of charge transfer, the d0→d1L, where L denotes a hole in the oxygen band. This finding may pave a different avenue for selectively manipulating specific types of order in complex materials of this class.
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| 10. |
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