SOLEIL Research Articles

An active x-ray beamstop based on single crystal CVD diamond at beamline SWING.

A compact active x-ray beamstop has been developed for the SWING beamline at Synchrotron SOLEIL with two main functions, blocking the x-ray beam directly transmitted by the sample to protect the Dectris EigerX4M 2D detector and monitoring its intensity. The beamstop is composed of a sensor inserted in a well of tungsten carbide. The sensor is based on a piece of free-standing single crystal chemical vapor deposited diamond used in the ionization chamber mode. The beamstop has been installed on the beamline detector stage within the detection vacuum chamber, just upstream of the large 2D detector. The intensity monitoring performance (rms noise over signal) is shown to be better than 0.06% and the linearity is shown to be better than 2% for over more than five decades. The beamstop has been calibrated between 5 and 16 keV to provide the photon flux measurements in absolute units (ph/s). The specific design of the beamstop increases the small-angle x-ray scattering q-range by a factor of 1.5 in the low angle side, as compared to the previous active beamstop, based on a more standard commercial Si diode. The beamstop has been available for three years for SWING user operation (5-17 keV). It is fully compatible with the different beamline operating modes and fluxes, except in the microbeam mode, where the very divergent beam becomes too large at the beamstop position, and the previous, larger, beamstop is then more appropriate.

A cluster source for photoelectron spectroscopy in VUV and X-ray ranges

A detailed description of a custom-made gas aggregation cluster source is given as well as of its coupling to permanent molecular beam end-stations of the beamlines DESIRS and PLEIADES at the French national facility synchrotron SOLEIL. Using (hydrated) hypoxanthine clusters as a case study, the production of clusters with different source parameters is discussed based on Vacuum Ultra-Violet (VUV) mass spectrometry. The ability of the cluster source to perform photoelectron spectroscopy is illustrated by photoelectron spectra obtained for valence and core shells.

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices

Context.Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices.Aims.We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from binary mixed ices:13CO:CH3OH ice and H2O:CH3OH ice.Methods.We irradiated these ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.Results.For13CO:CH3OH ice, CH3OH X-ray photodesorption yield is estimated to be ∼10−2molecule/photon at 564 eV. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is detected with a yield of ∼10−3molecule/photon. When methanol is mixed with water, X-ray photodesorption of methanol and of the previous COMs is not detected. X-ray induced chemistry, dominated by low-energy secondary electrons, is found to be the main mechanism that explains these results. We also provide desorption yields that are applicable to protoplanetary disk environments for astrochemical models.Conclusions.The X-ray emission from YSOs should participate in the enrichment of the protoplanetary disk gas phase with COMs such as methanol in the cold and X-ray dominated regions because of X-ray photodesorption from methanol-containing ices.

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices

Context.Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. This Paper I focuses on the case of X-ray photodesorption from pure methanol ices.Aims.We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from pure CH3OH ices, and to shed light on the mechanisms responsible for the desorption process.Methods.We irradiated methanol ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.Results.Under our experimental conditions, the CH3OH X-ray photodesorption yield from pure methanol ice is ~10−2molecule/photon at 564 eV. Photo-products such as CH4, H2CO, H2O, CO2, and CO also desorb at increasing efficiency. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is also detected. The physical mechanisms at play are discussed and must likely involve the thermalization of Auger electrons in the ice, thus indicating that its composition plays an important role. Finally, we provide desorption yields applicable to protoplanetary disk environments for astrochemical models.Conclusions.The X-rays are shown to be a potential candidate to explain gas-phase abundances of methanol in disks. However, more relevant desorption yields derived from experiments on mixed ices are mandatory to properly support the role played by X-rays in nonthermal desorption of methanol (see Paper II).

Characterization and performance evaluation of the XSPA-500k detector using synchrotron radiation.

Hybrid photon counting (HPC) detectors are widely used at both synchrotron facilities and in-house laboratories. The features of HPC detectors, such as no readout noise, high dynamic range, high frame rate, excellent point spread function, no blurring etc. along with fast data acquisition, provide a high-performance detector with a low detection limit and high sensitivity. Several HPC detector systems have been developed around the world. A number of them are commercially available and used in academia and industry. One of theimportant features of an HPC detector is a fast readout speed. Most HPC detectors can easily achieve over 1000 frames s-1, one or two orders of magnitude faster than conventional CCD detectors. Nevertheless, advanced scientific challenges require ever faster detectors in order to study dynamical phenomena in matter. The XSPA-500k detector can achieve 56 kframes s-1 continuously, without dead-time between frames. Using `burst mode', a special mode of the UFXC32k ASIC, the frame rate reaches 1 000 000 frames s-1. XSPA-500k was fully evaluated at the Metrology beamline at Synchrotron SOLEIL (France) and its readout speed was confirmed by tracking the synchrotron bunch time structure. The uniformity of response, modulation transfer function, linearity, energy resolution and other performance metrics were also verified either with fluorescence X-rays illuminating the full area of the detector or with the direct beam.

Reprint of: Pyrolysis of ethanol studied in a new high-repetition-rate shock tube coupled to synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy

Shock tube techniques for kinetic studies are continuously evolving driven by advances in kinetic modeling and detection techniques. An innovative category of shock tubes has been recently developed for use at Synchrotron facilities. In this work, a new high-repetition-rate shock tube (HRRST) was constructed to employ synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy (i2PEPICO) at the beamline DESIRS of the SOLEIL synchrotron. The shock tube design and performance (pressure profiles, repeatability of operations) are presented for the first time together with the detailed description of the coupling with the molecular beam end-station holding the i2PEPICO spectrometer. The first experimental results with the HRRST/i2PEPICO on ethanol pyrolysis are grouped based on four different experimental conditions, each highlighting functionality of this novel experimental system. Experiments were performed at temperatures between 1232 K and 1525 K, pressures between 6.2 bar and 7.5 bar, with 2.7% or 0.25% ethanol in argon, and photon energy of 10.0 eV or 11.0 eV. The results are supported by kinetic analyses with the CRECK model. This study shows the potential of the HRRST/i2PEPICO combination for obtaining detailed mechanistic and kinetic data for complex chemical systems. Mass spectra, photoelectron spectra and time-resolved species profiles were obtained for a wide variety of species from methyl radicals to large polyaromatic hydrocarbons. The different experimental conditions studied indicate how future experiments can be designed to target key regimes facilitating the elucidation of desired kinetic and mechanistic data.

The foreign-continuum absorption of water vapour in the far-infrared (50–500 cm−1)

We investigated the continuum absorption of water vapour diluted in nitrogen, oxygen and air in the range of the pure rotational band of the water molecule (50-500 cm−1). Spectra recordings were performed at room temperature with a Fourier transform spectrometer associated to a 151-m multipass gas cell located at the AILES beamline of SOLEIL synchrotron facility. The study includes the first laboratory measurements in the wide 90-330 cm−1 interval. Tests of the baseline stability, crucial for the continuum determination, are reported together with the expected pressure dependences of the continuum absorption, measured over different pressure ramps. Retrieved foreign-continuum cross-sections are found in good agreement with literature values available in the lower and upper parts of the studied frequency range. The reported results validate the MT_CKD foreign-continuum empirical model, widely used in atmospheric applications, even if some overestimation of the MT_CKD values is noted in the centre of the band where experimental data were absent.

N2-, O2- and Air-broadened half-widths and line shifts of methyl chloride in the 10 µm region

N2- and O2-broadening coefficients were measured at room temperature for 2914 ro-vibrational lines of methyl chloride in the region from 920 to 1140 cm−1 corresponding to the ν6 band, using a high-resolution Fourier transform spectrometer and a mono-spectrum non-linear least squares fitting of Voigt profiles. The spectra were recorded at the AILES beamline of the SOLEIL Synchrotron facility at various mixtures of CH3Cl with N2 or O2 gas. Broadening coefficients were retrieved for the two isotopes of CH3Cl from which we derived the air-broadenings. The rotational dependences of these coefficients were analyzed and modeled first using an empirical model, which reproduces the measurements within of about 5%. Pressure-induced shifts are also measured for about 375 and 418 transitions for O2- and N2-perturbers respectively with no obvious rotational dependence. The average absolute accuracies of the measurements are estimated to be about 7 and 17% for broadening and shift coefficients respectively. Comparisons are performed with previous measurements and next with semi-classical predictions achieved in this work. The entire set of results is given as Supplementary data Table for a use in spectroscopic databases and atmospheric detection.

Valence-shell photoelectron circular dichroism of ruthenium(III)-tris-(acetylacetonato) gas-phase enantiomers.

Chiral transition-metal complexes are of interest in many fields ranging from asymmetric catalysis and molecular materials science to optoelectronic applications or fundamental physics including parity violation effects. We present here a combined theoretical and experimental investigation of gas-phase valence-shell photoelectron circular dichroism (PECD) on the challenging open-shell ruthenium(III)-tris-(acetylacetonato) complex, Ru(acac)3. Enantiomerically pure Δ- or Λ-Ru(acac)3, characterized by electronic circular dichroism (ECD), were vaporized and adiabatically expanded to produce a supersonic beam and photoionized by circularly-polarized VUV light from the DESIRS beamline at Synchrotron SOLEIL. Photoelectron spectroscopy (PES) and PECD experiments were conducted using a double imaging electron/ion coincidence spectrometer, and compared to density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The open-shell character of Ru(acac)3, which is not taken into account in our DFT approach, is expected to give rise to a wide multiplet structure, which is not resolved in our PES signals but whose presence might be inferred from the additional striking features observed in the PECD curves. Nevertheless, the DFT-based assignment of the electronic bands leads to the characterisation of the ionized orbitals. In line with other recent works, the results confirm that PECD persists independently on the localization and/or on the achiral or chiral nature of the initial orbital, but is rather a probe of the molecular potential as a whole. Overall, the measured PECD signals on Ru(acac)3, a system exhibiting D3 propeller-type chirality, are of similar magnitude compared to those on asymmetric-carbon-based chiral organic molecules which constitute the vast majority of species investigated so far, thus suggesting that PECD is a universal mechanism, inherent to any type of chirality.

Pyrolysis of ethanol studied in a new high-repetition-rate shock tube coupled to synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy

Shock tube techniques for kinetic studies are continuously evolving driven by advances in kinetic modeling and detection techniques. An innovative category of shock tubes has been recently developed for use at Synchrotron facilities. In this work, a new high-repetition-rate shock tube (HRRST) was constructed to employ synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy (i 2 PEPICO) at the beamline DESIRS of the SOLEIL synchrotron. The shock tube design and performance (pressure profiles, repeatability of operations) are presented for the first time together with the detailed description of the coupling with the molecular beam end-station holding the i 2 PEPICO spectrometer. The first experimental results with the HRRST/i 2 PEPICO on ethanol pyrolysis are grouped based on four different experimental conditions, each highlighting functionality of this novel experimental system. Experiments were performed at temperatures between 1232 K and 1525 K, pressures between 6.2 bar and 7.5 bar, with 2.7% or 0.25% ethanol in argon, and photon energy of 10.0 eV or 11.0 eV. The results are supported by kinetic analyses with the CRECK model. This study shows the potential of the HRRST/i 2 PEPICO combination for obtaining detailed mechanistic and kinetic data for complex chemical systems. Mass spectra, photoelectron spectra and time-resolved species profiles were obtained for a wide variety of species from methyl radicals to large polyaromatic hydrocarbons. The different experimental conditions studied indicate how future experiments can be designed to target key regimes facilitating the elucidation of desired kinetic and mechanistic data.

Phase Transformation and Amorphization upon Alloys Magnesiation: Combining Operando X-Ray Diffraction and X-Ray Absorption Spectroscopy

Magnesium appears as a great alternative to lithium due to its high capacity, low cost, abundance and largely smaller reactivity compared to lithium [1]. Magnesium metal has however a tendency to react with conventional electrolytes to form a barrier on its surface [1], impeding cations exchange, and thus dramatically limiting reversible stripping/deposition of Mg. An interesting alternative is to replace Mg metal with negative electrode materials based on p-block elements (In, Sn, Sb, Bi...) as they electrochemically alloy with Mg and possess adequate stability in standard electrolytes [2]. These substitute electrodes can thus prove a promising solution to overcome the problem of compatibility with electrolytes, even if the reaction mechanisms behind their operation in conventional electrolytes remain partly unsolved.In a recent work, we investigated the electrochemical reactivity and performance of the InSb alloy as a negative electrode for Mg-ion batteries [3]. A strong synergy between In and Sb has been evidenced with the promotion of the electrochemical activity of Sb towards magnesiation/demagnesiation, in contrast to what was already reported for pure Sb electrodes where Mg2+ ions cannot be pulled out of the Mg3Sb2 phase after the first magnesiation [4].Using complementary information from operando X-Ray diffraction (XRD) and X-Ray Absorption Spectrosopy (XAS), we further characterized in-depth the electrochemical behavior of InSb to understand its peculiar performance. Operando XRD measurements demonstrate the formation of the Mg3Sb2 phase almost all along the first magnesiation, accompanied by the extrusion of In metal. While crystalline MgIn has always been detected in the case of pure In or InBi electrodes [5], we observed a kinetically dependent electrochemically-driven amorphization of MgIn. This behavior suggests a possible competition between crystallization and amorphization in the material. EXAFS data, obtained at the In and Sb K-edges at the ROCK beamline of synchrotron Soleil, corroborate the formation of Mg3Sb2 and In crystalline phases and the formation of MgIn, and give further insights on the atomic environement of In and Sb during the first magnesiation. Thanks to the evolution of EXAFS spectra as well as the changes in scattering paths, the phase proportions evolution as function of the number of Mg inserted into the alloy is followed.These results shed light on synergetic effects between p-block elements for Mg-ion batteries and more generally raise questions on the relation between in situ amorphization and electrochemical behavior. References : [1] Yoo et al., Energy Environ. Sci. 6, 2265–2279 (2013)[2] Zhang et al., Energy Storage Mater. 20, 118-38 (2019)[3] Murgia et al., Electrochim. Acta, 259, 276−283 (2018)[4] Blondeau et al., Phys. Chem. C 123, 1120–1126 (2019)[5] Murgia et al., Electrochim. Acta. 209, 730-736 (2016)Figure 1: Evolution of the phases concentrations at the In and Sb K-edges along the first magnesiation of a InSb/Mg cell. Figure 1

Determination of absolute O(3P) and O2(a1 Δ g) densities and kinetics in fully modulated O2 dc glow discharges from the O2(X3 Σ g −) afterglow recovery dynamics

A method is presented for the determination of the absolute densities of O(3P) atoms and O2(a1Δg) molecules in an O2 electrical discharge, which does not depend on any calibration procedure or knowledge of optical transition strengths. It is based on observing the recovery dynamics of the O2(X3Σg −) density in the afterglow of a fully-modulated discharge, and is demonstrated in a dc glow discharge in pure О2 at pressures of 0.2–4 Torr. The time-resolved O2(X3Σg −) density was measured by VUV absorption spectroscopy using the monochromator branch of the VUV DESIRS beamline at Synchrotron SOLEIL, but this methodology could be used with another density measurement technique. During the active discharge, the O2(X3Σg −) density is depleted by a combination of О2 dissociation, excitation into metastable states (principally O2(a1Δg)) and gas heating/dilation. After discharge extinction, the O2(X3Σg −) density progressively recovers to its initial (before discharge) value, with three distinct time-constants due to: (i) gas cooling (fast), (ii) O(3P) atom recombination (intermediate), and (iii) O2(a1Δg) quenching (slow). The O(3P) and O2(a1Δg) dynamics can be separated easily, allowing the O(3P) and O2(a1Δg) afterglow loss kinetics to be determined, as well as their mole fractions in the steady-state discharge. Both the O(3P) and O2(a1Δg) mole-fractions increase with current (up to the highest current studied, 40 mA) and pass through maxima with pressure at 1 Torr, reaching 16.5% and 8%, respectively. O(3P) atoms are principally lost by recombination at the borosilicate tube surface, with a loss probability in the afterglow of ∼8 × 10−4, nearly independent of gas pressure and discharge current (in contrast to previous observations in the active discharge []). The O2(a1Δg) dynamics were also measured by IR emission spectroscopy. In the late afterglow, this agrees well with the O2(X3Σg −) recovery dynamics, corresponding to an O2(a1Δg) surface loss probability of ∼2.2 × 10−4. The initial O2(a1Δg) loss is faster than in the later afterglow, indicating that it is also quenched by O atoms.

Backside-illuminated scientific CMOS detector for soft X-ray resonant scattering and ptychography.

The impressive progress in the performance of synchrotron radiation sources is nowadays driven by the so-called `ultimate storage ring' projects which promise an unprecedented improvement in brightness. Progress on the detector side has not always been at the same pace, especially as far as soft X-ray 2D detectors are concerned. While the most commonly used detectors are still based on microchannel plates or CCD technology, recent developments of CMOS (complementary metal oxide semiconductor)-type detectors will play an ever more important role as 2D detectors in the soft X-ray range. This paper describes the capabilities and performance of a camera equipped with a newly commercialized backside-illuminated scientific CMOS (sCMOS-BSI) sensor, integrated in a vacuum environment, for soft X-ray experiments at synchrotron sources. The 4 Mpixel sensor reaches a frame rate of up to 48 frames s-1 while matching the requirements for X-ray experiments in terms of high-intensity linearity (>98%), good spatial homogeneity (<1%), high charge capacity (up to 80 ke-), and low readout noise (down to 2 e- r.m.s.) and dark current (3 e- per second per pixel). Performance evaluations in the soft X-ray range have been carried out at the METROLOGIE beamline of the SOLEIL synchrotron. The quantum efficiency, spatial resolution (24 line-pairs mm-1), energy resolution (<100 eV) and radiation damage versus the X-ray dose (<600 Gy) have been measured in the energy range from 40 to 2000 eV. In order to illustrate the capabilities of this new sCMOS-BSI sensor, several experiments have been performed at the SEXTANTS and HERMES soft X-ray beamlines of the SOLEIL synchrotron: acquisition of a coherent diffraction pattern from a pinhole at 186 eV, a scattering experiment from a nanostructured Co/Cu multilayer at 767 eV and ptychographic imaging in transmission at 706 eV.

Velocity Map Imaging VUV Angle-Resolved Photoemission on Isolated Nanosystems: Case of Gold Nanoparticles

We present an angle-resolved photoelectron spectroscopy study on isolated gold nanoparticles in the photon energy range between 6 and 12 eV performed at the DESIRS beamline of Synchrotron SOLEIL wi...

Vibrationally and Spin-Orbit-Resolved Inner-Shell X-ray Absorption Spectroscopy of the NH+ Molecular Ion: Measurements and ab Initio Calculations

This article presents N2+ fragment yields following nitrogen K-shell photo-absorption in the NH+ molecular ion measured at the SOLEIL synchrotron radiation facility in the photon energy region 390–450 eV. The combination of the high sensitivity of the merged-beam, multi-analysis ion apparatus (MAIA) with the high spectral resolution of the PLEIADES beamline helped to resolve experimentally vibrational structures of highly excited [N1s−1H]*+ electronic states with closed or open-shell configurations. The assignment of the observed spectral features was achieved with the help of density functional theory (DFT) and post-Hartree Fock Multiconfiguration Self-Consistent-Field/Configuration Interaction (MCSCF/CI) ab-initio theoretical calculations of the N1s core-to-valence and core-to-Rydberg excitations, including vibrational dynamics. New resonances were identified compared to previous work, owing to detailed molecular modeling of the vibrational, spin-orbit coupling and metastable state effects on the spectra. The latter are evidenced by spectral contributions from the 4Σ− electronic state which lies 0.07 eV above the NH+2Π ground state.

Fourier-Transform VUV Spectroscopy of 14,15N and 12,13C

Accurate Fourier-transform spectroscopic absorption measurements of vacuum ultraviolet transitions in atomic nitrogen and carbon were performed at the Soleil synchrotron. For 14N, transitions from the 2s22p34S3/2 ground state and from the 2s22p32P and 2D metastable states were determined in the 95–124 nm range at an accuracy of 0.025cm−1. The combination of these results with data from previous precision laser experiments in the vacuum ultraviolet range reveals an overall and consistent offset of −0.04 cm−1 from values reported in the NIST database. The splittings of the 2s22p34S3/2 – 2s2p44PJ transitions are well-resolved for 14N and 15N and the isotope shifts determined. While excitation of a 2p valence electron yields very small isotope shifts, excitation of a 2s core electron results in large isotope shifts, in agreement with theoretical predictions. For carbon, six transitions from the ground 2s22p23PJ and 2s22p3s3PJ excited states at 165 nm are measured for both 12C and 13C isotopes.

Direct measurements of electronic ground state ro-vibrationally excited D2 molecules produced on ECR plasma-facing materials by means of VUV-FT absorption spectroscopy

Ro-vibrationally excited molecules of deuterium are involved in non-equilibrium chemical reactions in divertor region of tokamak (see molecular assisted recombination) or in neutral beam injector to produce negative ion (see dissociative electron attachment) for fusion plasmas. These molecules produced both in a plasma volume and on surfaces are no longer in their electronic ground state X1∑g+(v”⩾0,J”) and populate non-uniformly different vibrational (v″) and rotational levels (J″). The high resolution VUV Fourier Transform spectrometer of the DESIRS beam line (SOLEIL synchrotron) is applied to directly scrutinize the ro-vibrationally excited levels of the D2 ground state from v″ = 0 to 10 and J″ up to 8 in an electron cyclotron resonance (ECR) cold plasma. This is performed for different plasma-facing materials, i.e. quartz, tantalum, tungsten, and stainless steel, in order to compare their relative impact in molecular excitation through recombinative desorption from surfaces. A significant effect of these materials on the absolute distribution of the vibrationally states has been found above v″ > 3. The experimental detection limit for Quartz is v″ = 7 whereas tungsten and stainlees steel excite the molecules up to v″ = 9 and tantalum up to v″ = 10. The use of a bare, temperature-controlled surface of Quartz as a reference, compared to metallic surfaces, allows us to determine the relative production of these excited levels. The recombinative desorption rate on tungsten and stainless steel compared to quartz is ~ 2.6 higher and reaches ~ 5 for tantalum.

Lattice Strain Evolutions in Ni-W Alloys during a Tensile Test Combined with Synchrotron X-ray Diffraction.

Ni and Ni(W) solid solution of bulk Ni and Ni-W alloys (Ni-10W, Ni-30W, and Ni-50W) (wt%) were mechanically compared through the evolution of their {111} X-ray diffraction peaks during in situ tensile tests on the DiffAbs beamline at the Synchrotron SOLEIL. A significant difference in terms of strain heterogeneities and lattice strain evolution occurred as the plastic activity increased. Such differences are attributed to the number of brittle W clusters and the hardening due to the solid solution compared to the single-phase bulk Ni sample.

Astrochemical relevance of VUV ionization of large PAH cations.

As a part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by the interaction with vacuum ultra-violet (VUV) photons that are emitted by hot young stars. This interaction leads to the emission of the well-known aromatic infrared bands but also of electrons, which can significantly contribute to the heating of the interstellar gas. Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9 to 20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy. Photoionization is found to be predominant over dissociation at all energies, which differs from an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size. Large PAH cations could be efficiently ionized in H i regions and provide a contribution to the heating of the gas by photoelectric effect. Also, at the border of or in H ii regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points.

Reevaluation of metal interconnectivity in a partially molten silicate matrix using 3D microtomography

Understanding metal-silicate differentiation in small rocky bodies that accreted early in solar system history requires quantification of the effects of variable amounts of silicate melt and molten metal on the connectivity of metal-rich liquids. To shed light on this question, the equilibrium geometry and textural ripening of metal grains in the vicinity of the metal interconnection threshold have been determined experimentally. High pressure and temperature experiments were performed in the three-phase system forsterite + silicate melt + nickel at conditions of 1 GPa and up to 2080 K using piston-cylinder and Paris-Edinburgh presses. Sample textures were analyzed by 3D X-Ray microtomography either in-situ at the PSICHE beamline of the SOLEIL synchrotron, or on quenched samples using a laboratory Computed Tomography scan. Although dihedral angles point to textural equilibrium at the scale of individual grains at the end of each experiment, the attainment of textural equilibrium at sample scale is not straightforward. Depending on the relative proportions of the phases, different states of textural maturation are revealed. A particularly important issue is that time-resolved in-situ microtomography data show that cold (subsolidus) compression at the beginning of the experiment leads to soft metal grains being squeezed between silicates, leading to a forced interconnectivity of nickel. High temperature experiments with metal contents ≤20 vol% resulted in disruption of these forced networks, while the networks persisted in time for metal contents ≥25 vol%. This is taken to indicate that the stable interconnection threshold of pure nickel in a partially molten silicate matrix lies between 20 and 25 vol%. Therefore, we conclude that care must be taken when defining the interconnection threshold: not only should there be existence of a network of touching grains, but this network must persist in time in the absence of external forces and at pressure-temperature conditions that permit grain-boundary movement (i.e. excluding kinetically arrested systems). Growth of silicate grains is identified as the process driving textural maturation, and may explain the variability of interconnection thresholds reported in the literature. In addition, these considerations shed light on the diversity of textures observed in natural meteoritic samples (e.g. carbonaceous and ordinary chondrites and primitive achondrites), providing textural arguments to constrain the processes that affected these meteorites.