A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources

Kunnus, Kristjan; Rajković, Ivan; Schreck, Simon; Quevedo, Wilson; Eckert, Sebastian; Beye, Martin; Suljoti, Edlira; Weniger, Christian; Kalus, Christian K.; Grübel, S.; Scholz, Mirko; Nordlund, Dennis; Zhang, Wenkai; Hartsock, Robert J.; Gaffney, Kelly J.; Schlotter, W. F.; Turner, Joshua J.; Kennedy, Brian; Hennies, Franz; Techert, Simone; Wernet, Philippe; Föhlisch, Alexander

doi:10.1063/1.4772685

Cited by 74 publications

(74 citation statements)

References 35 publications

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“…The experimental setup (FlexRIXS) with an in-vacuum liquid jet for sample delivery and a grazing incidence spherical grating Rowland spectrometer was described before. 31 Briefly, the spectrometer was operated in a slitless mode to increase the geometric acceptance, with the 20 µm jet diameter limiting the resolving power. The incident X-rays were linearly polarized and the emitted X-rays were detected in-plane of the incident polarization under 90° scattering angle.…”

Section: Methodsmentioning

confidence: 99%

“…Only relatively recently in-vacuum methods for soft X-ray RIXS spectroscopy on liquids and solutions were developed [27][28][29][30][31] and typical count rates are low due to the small fluorescence yields and the considerable solvent absorption in the soft X-ray range. The latter is particularly important when dealing with dilute samples as typical for chemically/biologically relevant samples.…”

Section: Introductionmentioning

confidence: 99%

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Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

et al. 2016

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Abstract:The valence excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped with resonant inelastic X-ray scattering (RIXS) at the Fe L2,3-and N K-edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligandto-metal and metal-to-ligand charge transfer excited states. Ab initio calculations utilizing the RASPT2 method was used to simulate the Fe L2,3-edge RIXS spectra and enabled quantification of the covalency of both occupied and empty orbitals of π and σ symmetry. We find that π back-donation in the ferric complex is smaller compared to the ferrous complex. This is evidenced by the relative amount of Fe 3d character in the nominally 2π CN -molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L3-edge RIXS to the Fe 3d character in the occupied molecular orbitals we also find that the donation interactions are dominated by σ-bonding. The latter is found to be stronger in the ferric complex with a Fe 3d contribution to the nominally 5σ CN -molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

et al. 2016

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“…The experiments were performed at the beamline U41_PGM and U49/2-PGM 1 of the synchrotron radiation source at the Helmholtz Zentrum Berlin using the FlexRIXS [38] and Transmission NEXAFS [39] endstations and at P04 of PETRA III at DESY site in Hamburg using the ChemRIXS endstation. X-ray absorption measurements in transmission mode were performed with a liquid cell [38].…”

Section: Methodsmentioning

confidence: 99%

Ionic Solutions Probed by Resonant Inelastic X-ray Scattering

Yin

Rajković

Veedu

et al. 2015

Zeitschrift Für Physikalische Chemie

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X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction.

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“…%) was delivered to the interaction region using the Liquid Jet End Station, which consists of a liquid microjet in a differentially pumped high vacuum (2 × 10 −3 millibars at the jet, 4×10 −7 millibars at the detector) and a Graze spectrometer XES 350 38 mounted at 90 • with respect to the incident x-ray beam, as described in detail elsewhere. 39 The liquid microjet was produced by a gas-dynamic virtual nozzle 40 (GDVN) operated at 800 psi liquid pressure and 330 psi He gas pressure. The microjet underwent Rayleigh breakup 41 after a few hundred microns, driven by a piezoelectric actuator at 900 kHz (sine wave with 50 V amplitude), producing a singlefile train of uniform droplets with a diameter of 5 µm, droplet spacing of 16 µm, and droplet speed of 14 m/s.…”

Section: A Experimental Setup At the Soft X-ray Materials Science (Smentioning

confidence: 99%

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

Sellberg

McQueen

Laksmono

et al. 2015

The Journal of Chemical Physics

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The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T H ) of ∼232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b 1 ′ and 1b 1 ′′ peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important. C 2015 AIP Publishing LLC. [http://dx

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A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources

Cited by 74 publications

References 35 publications

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

Ionic Solutions Probed by Resonant Inelastic X-ray Scattering

X-ray emission spectroscopy of bulk liquid water in “no-man’s land”

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