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Register a new userMolecular Isomer Identification of Titan Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation
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The chemical composition of Titan organic haze is poorly known. To address this issue, laboratory analogs named tholins are synthesized, and analyzed by methods requiring often an extraction process in a carrier solvent. These methods exclude the analysis of the insoluble tholins fraction and assume a hypothetical chemical equivalence between soluble and insoluble fractions. In this work, we present a powerful complementary analysis method recently developed on the DESIRS VUV synchrotron beamline at SOLEIL. It involves a soft pyrolysis of tholins at ~230 deg C and an electron ion coincidence analysis of the emitted volatiles compounds photoionized by the tunable synchrotron radiation. By comparison with reference photoelectron spectra (PES), the spectral information collected on the detected molecules yields their isomeric structure. The method is more readily applied to light species, while for heavier ones the number of possibilities and the lack of PES reference spectra in the literature limit its analysis. A notable pattern in the analyzed tholins is the presence of species containing adjacent doubly-bonded N atoms, which might be a signature of heterogeneous incorporation of N2 in tholins.
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Titan, the biggest moon of Saturn, has a thick atmosphere which presents similarities with the one thought to be on Earth at its beginning. The study of Titan s photochemical haze is thus a precious tool in gaining knowledge of the primitive atmosphere of Earth. The chemistry occurring in Titan s atmosphere and the exact processes at act in the formation of the hazes remain largely unknown. The production of analogs samples on Earth has proved to be a useful tool to improve our knowledge of the aerosols formation on Titan. Such solid organic analogs samples, named tholins, were produced with the PAMPRE experiment (French acronym for Aerosols Microgravity Production by Reactive Plasma). PAMPRE tholins were found to be mostly insoluble, with only one-third of the bulk sample that can be dissolved in methanol. This partial solubility limited the previous studies in mass spectrometry, which were done only on the soluble fraction. The goal of the present study is to compare the two fractions of PAMPRE s tholins (insoluble and soluble) using a ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometer (FTICR) equipped with a laser desorption/ionization source. Using modified Van Krevelen diagrams, we compare the global distribution of the molecules within the samples according to their Hydrogen/Carbon ratio and Nitrogen/Carbon ratio. Major differences are observed in the molecular composition of the soluble and the insoluble fraction. The soluble fraction of tholins was previously identified as a set of polymers of average formula (C2H3N)n. In this work we observe that the insoluble fraction of tholins is comprised of a significantly different set of polymers with an average composition of (C4H3N2)n.
Numerous studies have been carried out to characterize the chemical composition of laboratory analogues of Titan aerosols (tholins), but their molecular composition as well as their structure are still poorly known. If pyrolysis gas chromatography mass spectrometry (pyr-GCMS) has been used for years to give clues about this composition, the highly disparate results obtained can be attributed to the analytical conditions used and/or to differences in the nature of the analogues studied. In order to have a better description of Titan tholins molecular composition, we led a systematic analysis of these materials using pyr-GCMS with two major objectives: (i) exploring the analytical parameters to estimate the biases this technique can induce and to find an optimum for analyses allowing the detection of a wide range of compounds and thus a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio in the gaseous reactive medium on the tholins molecular structure. With this aim, we used a radio-frequency plasma discharge to synthetize tholins with different concentrations of CH4 diluted in N2. The samples were systematically pyrolyzed from 200 to 600{deg}C. The extracted gases were then analyzed by GCMS for their molecular identification.
Volatile organic molecules formed by photochemistry in the upper atmosphere of Titan can undergo condensation as pure ices in the stratosphere and the troposphere as well as condense as ice layers onto the organic aerosols that are visible as the haze layers of Titan. As solar photons penetrate through Titan s atmosphere, shorter-wavelength photons are attenuated and longerwavelength photons make it into the lower altitudes, where aerosols become abundant. We conducted an experimental study to evaluate the long wavelength ( > 300 nm) photo-reactivity of these ices accreted on the Titan aerosol-analogs (also known as tholins) made in the laboratory. We have focused on acetylene, the third most abundant hydrocarbon in Titan s atmosphere after CH4 and C2H6. Further, acetylene is the most abundant unsaturated hydrocarbon in Titan s atmosphere. Our results indicate that the aerosols can act as activation centers to drive the photoreactivity of acetylene with the aerosols at the accretion interface at wavelengths where acetylene-ice alone does not show photoreactivity. We found that along with photochemistry, photodesorption plays an important role. We observed that about 15% of the initial acetylene is photodesorbed, with a photodesorption rate of (2.1 +/- 0.2) x 10-6 molecules.photon-1 at 355 nm. This photodesorption is wavelength-dependent, confirming that it is mediated by the UV absorption of the aerosol analogues, similar to photochemistry. We conclude that the UV-Vis properties of aerosols would determine how they evolve further in Titan s atmosphere and on the surface through photochemical alterations involving longer wavelength photons.
Ultrafast dynamical processes in photoexcited molecules can be observed with pump-probe measurements, in which information about the dynamics is obtained from the transient signal associated with the excited state. Background signals provoked by pump and/or probe pulses alone often obscure these excited state signals. Simple subtraction of pump-only and/or probe-only measurements from the pump-probe measurement, as commonly applied, results in a degradation of the signal-to-noise ratio and, in the case of coincidence detection, the danger of overrated background subtraction. Coincidence measurements additionally suffer from false coincidences. Here we present a probabilistic approach based on Bayesian probability theory that overcomes these problems. For a pump-probe experiment with photoelectron-photoion coincidence detection we reconstruct the interesting excited-state spectrum from pump-probe and pump-only measurements. This approach allows to treat background and false coincidences consistently and on the same footing. We demonstrate that the Bayesian formalism has the following advantages over simple signal subtraction: (i) the signal-to-noise ratio is significantly increased, (ii) the pump-only contribution is not overestimated, (iii) false coincidences are excluded, (iv) prior knowledge, such as positivity, is consistently incorporated, (v) confidence intervals are provided for the reconstructed spectrum, and (vi) it is applicable to any experimental situation and noise statistics. Most importantly, by accounting for false coincidences, the Bayesian approach allows to run experiments at higher ionization rates, resulting in a significant reduction of data acquisition times. The application to pump-probe coincidence measurements on acetone molecules enables novel quantitative interpretations about the molecular decay dynamics and fragmentation behavior.
Time-resolved pump-probe measurements of Xe, pumped at 133~nm and probed at 266~nm, are presented. The pump pulse prepared a long-lived hyperfine wavepacket, in the Xe $5p^5(^2P^{circ}_{1/2})6s~^2[1/2]^{circ}_1$ manifold ($E=$77185 cm$^{-1}=$9.57 eV). The wavepacket was monitored via single-photon ionization, and photoelectron images measured. The images provide angle- and time-resolved data which, when obtained over a large time-window (900~ps), constitute a precision quantum beat spectroscopy measurement of the hyperfine state splittings. Additionally, analysis of the full photoelectron image stack provides a quantum beat imaging modality, in which the Fourier components of the photoelectron images correlated with specific beat components can be obtained. This may also permit the extraction of isotope-resolved photoelectron images in the frequency domain, in cases where nuclear spins (hence beat components) can be uniquely assigned to specific isotopes (as herein), and also provides phase information. The information content of both raw, and inverted, image stacks is investigated, suggesting the utility of the Fourier analysis methodology in cases where images cannot be inverted.
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