Molecular Isomer Identification of Titan’s Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation

Miranda, Barbara Cunha de; Garcia, Gustavo A.; Gaie-Levrel, François; Mahjoub, Ahmed; Gautier, Thomas; Fleury, Benjamin; Nahon, Laurent; Pernot, Pascal; Carrasco, Nathalie

doi:10.1021/acs.jpca.6b03346

Cited by 10 publications

(13 citation statements)

References 97 publications

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“…Diazo and triazo species however, are not taken into account and their implications on the gas phase chemistry are poorly understood with respect to the nitrogen-rich tholins. Two previous studies by Gautier et al (2011) andCunha de Miranda et al (2016) on the gas phase and solid tholin material produced in the PAMPRE reactor can be clues to this conundrum. Gautier et al (2011) first identified C 4 H 3 N 5 (Tetrazolo[1,5-b]pyridazine) as the main aromatic gas phase product using gas chromatography.…”

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 95%

“…This heteroaromatic compound contains multiple single or double bonded nitrogen atoms. Furthermore, Cunha de Miranda et al (2016) revealed the presence of heteroaromatic structures present in tholins such as triazole rings (C 2 H 3 N 3 ). This compound, along with the cyclic diazirine c-CH 2 N 2 or cyanamide H 2 N -CN, were shown to be strong candidates for the observed N --N patterns.…”

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

“…A candidate molecule within this mass range potentially available for the initiation of further pathways is CH 2 N 2 (e.g. He and Smith 2014;Cunha de Miranda et al 2016), for which three isomeric forms are considered here: diazomethane CH 2 N 2 , cyclic diazirine c-CH 2 N 2 and cyanamide H 2 N -CN. CH 2 N 2 was previously excluded from the composition of tholins by Cunha de Miranda et al (2016), while both cyclic diazirine and cyanamide have been identified among several nitrogenous prebiotic organic compounds present in tholins Smith 2013, 2014;Cunha de Miranda et al 2016).…”

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

“…He and Smith 2014;Cunha de Miranda et al 2016), for which three isomeric forms are considered here: diazomethane CH 2 N 2 , cyclic diazirine c-CH 2 N 2 and cyanamide H 2 N -CN. CH 2 N 2 was previously excluded from the composition of tholins by Cunha de Miranda et al (2016), while both cyclic diazirine and cyanamide have been identified among several nitrogenous prebiotic organic compounds present in tholins Smith 2013, 2014;Cunha de Miranda et al 2016). Formation of linear CH 2 N 2 (diazomethane) following 1 CH 2 + N 2 −→ CH 2 N 2 was shown by Braun et al (1970) to be significant only for high pressures not relevant to our experimental setup nor to Titan's upper atmosphere conditions.…”

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

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Nitrogen-containing Anions and Tholin Growth in Titan’s Ionosphere: Implications for Cassini CAPS-ELS Observations

Dubois

Carrasco

Bourgalais

et al. 2019

ApJL

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The Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) instrument onboard Cassini revealed an unexpected abundance of negative ions above 950 km in Titan's ionosphere. In situ measurements indicated the presence of negatively charged particles with mass-over-charge ratios up to 13,800 u/q. At present, only a handful of anions have been characterized by photochemical models, consisting mainly of C n H − carbon chain and C n−1 N − cyano compounds (n = 2 − 6); their formation occurring essentially through proton abstraction from their parent neutral molecules. However, numerous other species have yet to be detected and identified. Considering the efficient anion growth leading to compounds of thousands of u/q, it is necessary to better characterize the first light species. Here, we present new negative ion measurements with masses up to 200 u/q obtained in an N 2 :CH 4 dusty plasma discharge reproducing analogous conditions to Titan's ionosphere. We perform a comparison with high altitude CAPS-ELS measurements near the top of Titan's ionosphere from the T18 encounter. The main observed peaks are in agreement with the observations. However, a number of other species (e.g. CNN -, CHNN -) previously not considered suggests an abundance of N-bearing compounds, containing two or three nitrogen atoms, consistent with certain adjacent doubly-bonded nitrogen atoms found in tholins. These results suggest that an N-rich incorporation into tholins may follow mechanisms including anion chemistry, further highlighting the important role of negative ions in Titan's aerosol growth.

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Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 95%

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

Section: Spectra Analysis Of Light and Intermediate N-rich Anionsmentioning

confidence: 99%

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Nitrogen-containing Anions and Tholin Growth in Titan’s Ionosphere: Implications for Cassini CAPS-ELS Observations

Dubois

Carrasco

Bourgalais

et al. 2019

ApJL

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“…Even more interesting from the analytical point of view is the combination of angle-resolved photoemission (ARPES) with ion mass spectrometry or full momentum imaging. In the past years, single-and double-imaging coincidence techniques have been used to determine the composition of complex media, such as flames [94][95][96], smog chambers [97], or planetary aerosols [98], by mass-selected multiplex photoelectron spectroscopy to determine the isomeric composition of a given compound having a signature in the mass spectrum. One could easily add the PECD information so that, apart from the structure, e.es.…”

Section: Overview On Pecd: Case Of Fenchone and Camphor 21 Formalismmentioning

confidence: 99%

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

Hadidi

Božanić

Garcia

et al. 2018

Advances in Physics: X

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Photoelectron circular dichroism (PECD) is an intense orbital-specific chiroptical effect observed as asymmetries in the angular distribution of photoelectrons produced by photoionization of randomly oriented pure enantiomers with circularly polarized light. After a broad introduction placing this effect in the context of new physical chiralsensitive methods, we review the main characteristics of PECD in terms of molecular photoionization dynamics. We stress also the analytical capabilities of PECD to retrieve enantiomeric excesses (e.es.) and to probe subtle details of the whole molecular potential, some of them exemplified by the showcase camphor and fenchone molecules. We then present the case of the amino acid alanine for which an interplay between PECD and conformer population is rationalized. Based on this study, we propose a photophysical astrophysical scenario for the origin of life's homochirality, relying upon the asymmetry of the associated recoiling alanine parent ion that could lead at the relevant Lyman-α energy to an e.e. of up to 4% in a given line of sight, which appears independent of the temperature. In an attempt to generalize this scenario to other amino acids, new data on proline showing an e.e. of 12%, of the same sign as alanine, are also presented.

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High‐resolution mass spectrometry for future space missions: Comparative analysis of complex organic matter with LAb‐CosmOrbitrap and laser desorption/ionization Fourier transform ion cyclotron resonance

Selliez¹,

Maillard

Cherville³

et al. 2020

Rapid Comm Mass Spectrometry

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(RATIONALE) Mass spectrometers are regularly boarded on spacecraft for the exploration of the Solar System. A better understanding of the origin, distribution and evolution of organic matter and its relationships with inorganic matter in different extra-terrestrial environments requires the development of innovative space tools, described as Ultra High Resolution Mass Spectrometry (UHRMS) instruments. (METHODS) Analyses of a complex organic material simulating extraterrestrial matter (Titan's tholins) are performed with a homemade space-designed Orbitrap TM equipped with a laser ablation ionization source at 266 nm: the LAb-CosmOrbitrap. Mass spectra are obtained using only one laser shot and transient duration of 838 ms. A comparison is made on the same sample with a laboratory benchmark mass spectrometer: a Fourier Transform Ion Cyclotron Resonance equipped with a laser desorption ionization at 355 nm (LDI-FTICR) allowing accumulation of 20,000 laser shots. (RESULTS) Mass spectra and attributions of molecular formulae based on the peaks detected by both techniques show significant similarities. Detection and identification of the same species are validated. The formation of clusters ions with the LAb-CosmOrbitrap is also presented. This specific feature brings informative and unusual indirect detections about the chemical compounds constituting Titan's tholins. In particular, the detection of HCN confirms previous results obtained with laboratory Electrospray Ionization (ESI)-UHRMS studies about the understanding of polymeric patterns for the formation of tholins. (CONCLUSION) Capabilities of the LAb-CosmOrbitrap to decipher complex organic mixtures using single laser shot and a short transient are highlighted. In agreement with results provided by a commercial FTICR instrument in the laboratory, we demonstrate in this work the relevance of a space laser-CosmOrbitrap instrument for the future planetary exploration.

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Molecular Isomer Identification of Titan’s Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation

Cited by 10 publications

References 97 publications

Nitrogen-containing Anions and Tholin Growth in Titan’s Ionosphere: Implications for Cassini CAPS-ELS Observations

Nitrogen-containing Anions and Tholin Growth in Titan’s Ionosphere: Implications for Cassini CAPS-ELS Observations

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

High‐resolution mass spectrometry for future space missions: Comparative analysis of complex organic matter with LAb‐CosmOrbitrap and laser desorption/ionization Fourier transform ion cyclotron resonance

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