Résumé: The Markov, as well as the secular, approximations are key assumptions that have been widely used to model decoherence in a large variety of open quantum systems, but, as far as intermolecular collisions are considered, very little has been done in the time domain. In order to probe the limits of both approximations, we here study the influence of pressure on the alignment revivals (echoes) created in properly chosen gas mixtures (HCl and CO 2 , pure and diluted in He) by one (two) intense and short laser pulse(s). Experiments and direct predictions using molecular-dynamics simulations consistently demonstrate, through analyses at very short times ( < 15 ps ) after the laser kick(s), the breakdown of these approximations in some of the selected systems. We show that the nonadiabatic laser-induced molecular alignment technique and model used in this paper directly provide detailed information on the physical mechanisms involved in the collisional dissipation. Besides this “fundamental” interest, our findings also have potential practical applications for radiative heat transfer in planetary atmospheres and climate studies. Indeed, short time delays in the dipole autocorrelation function monitoring the light absorption spectrum correspond to large detunings from the optical resonances in the frequency domain, thus influencing the atmospheric transparency windows. Furthermore, the fact that the approach tested here for linear rotors can potentially be applied to almost any gas mixture (including, for instance, nonlinear and/or reacting molecules) further strengthens and broadens the perspectives that it opens.

Résumé: Context. The assignment of the mid-infrared (mid-IR) emission features and plateaus observed in C-rich and H-rich regions of the interstellar medium (ISM) is still debated. Such mid-IR assignments must also be related to their contribution to the extinction curve in our galaxy and to the ultraviolet (UV) bump. Aims. The aim of this work is to investigate the influence of hydrogenation rate on the mid-IR spectra of populations of carbon clusters in order to constraint the nH/nC ratios in regions of the ISM where carbon is an important component. Their potential contribution to the extinction curve and in particular to the UV bump is also investigated. Methods. The absorption IR and optical spectra of tens of thousands of C24Hn (n = 0, 6, 12, 18, 24) isomers classified into structural families – namely flakes, branched, pretzels, and cages – were computed using the density functional based tight binding electronic structure method and its time-dependent version, respectively. Final spectra were obtained by averaging the spectra of many individual isomers. Results. The shapes and the relative intensities of the bands centered at ~3.25 and 3.40 µm and assigned to the C–H stretch of sp2 and sp3 carbon atoms, respectively, present a clear dependence on the nH/nC ratio. From a comparison with the astronomical spectrum from the Orion bar H2S1, the most interesting emitting candidates would pertain to the flakes population; this is the most energetically favorable family of clusters, possessing a high content of five and six carbon rings and being mostly planar, with no sp1 carbon atoms and with a nH/nC ratio of lower than 0.5. The same conclusion is drawn when comparing the computed IR features in the [4–20 µm] region with the observed plateaus from some C-rich and H-rich planetary nebulae objects of the Small Magellanic Cloud. The contribution of the same family could be considered for the UV bump. When nH/nC increases, only a contribution to the high-energy part of the continuum due to σ → π✶ excitations can reasonably be considered. Conclusions. These results bring some constraints on the structural features and on the nH/nC ratio of the hydrogenated carbon populations emitting in the mid-IR domain in interstellar objects such as protoplanetary and reflection nebulae. The flakes population, with a low nH/nC ratio, is an interesting candidate for the carbon population emitting in these regions, but not for that absorbing in the diffuse ISM. None of the populations studied in the present work can account for the UV bump, but they would contribute to a broad extinction rise in this domain. The computed features reported in this article could be used to interpret future astronomical data provided by the James Webb Space Telescope.

Résumé: Aminoacetonitrile is an interstellar molecule with a prominent prebiotic role, already detected in the chemically-rich molecular cloud Sagittarius B2(N) and postulated to be present in the atmosphere of the largest Saturn's moon, Titan. To further support its observation in such remote environments and laboratory experiments aimed at improving our understanding of interstellar chemistry, we report a thorough spectroscopic and structural characterization of aminoacetonitrile. Equilibrium geometry, fundamental bands as well as spectroscopic and molecular parameters have been accurately computed by exploiting a composite scheme rooted in the coupled-cluster theory that accounts for the extrapolation to the complete basis set limit and core-correlation effects. In addition, a semi-experimental approach that combines ground-state rotational constants for different isotopic species and calculated vibrational corrections has been employed for the structure determination. From the experimental side, we report the analysis of the three strongest fundamental bands of aminoacetonitrile observed between 500 and 1000 cm−1 in high-resolution infrared spectra. More generally, all computed band positions are in excellent agreement with the present and previous experiments. The only exception is the ν15 band, for which we provide a revision of the experimental assignment, now in good agreement with theory.

Résumé: Line coupling and line mixing effects in parallel and perpendicular bands of CH3D perturbed by N2 have been studied. The work focuses on exhibiting the j and k dependencies of these two processes. The calculations were based on a previously reported anisotropic intermolecular potential including both the long-range multipole, induction, and dispersion forces and a short-range atom-atom model. It is shown that components with L1 = 3 of the atom-atom model are dominant contributions to the diffusion operator. As a consequence, in comparison with other molecular systems such as the CH3Cl-N2 and CH3I-N2, theoretically predicted line coupling and line mixing effects exhibit completely new j and k dependencies. In general, the theoretically calculated halfwidths and intra-doublets’ off-diagonal elements of the relaxation matrix are in reasonable agreement with measurements.

Résumé: Icy grain mantles are the main reservoir of the volatile elements that link chemical processes in dark, interstellar clouds with the formation of planets and the composition of their atmospheres. The initial ice composition is set in the cold, dense parts of molecular clouds, before the onset of star formation. With the exquisite sensitivity of the James Webb Space Telescope, this critical stage of ice evolution is now accessible for detailed study. Here we show initial results of the Early Release Science programme Ice Age that reveal the rich composition of these dense cloud ices. Weak ice features, including 13CO2, OCN−, 13CO, OCS and complex organic molecule functional groups, are now detected along two pre-stellar lines of sight. The 12CO2 ice profile indicates modest growth of the icy grains. Column densities of the major and minor ice species indicate that ices contribute between 2% and 19% of the bulk budgets of the key C, O, N and S elements. Our results suggest that the formation of simple and complex molecules could begin early in a water-ice-rich environment.

Résumé: Abstract The way in which molecules can arrange themselves is at the root of organic chemistry and elucidating the structures present in isomeric mixtures remains a major challenge nowadays. A tantalizing question for chemists is how molecules transform from one structural configuration to another one. This review introduces in details a technique?tunable photoionization chemical monitoring?that couples tandem mass spectrometry and photoionization enabling to answer the two aforementioned questions for molecular ions. It is based on tracking reactivity changes in bimolecular ion?molecule reactions as a function of the internal energy of the ions. This is illustrated with (i) the structural elucidation of ortho-benzyne distonic cation within a C6H4+$$ {}_6{H_4}^{+} $$ population and (ii) the tracking of the isomerization from azulene radical cation as it gets gradually energized to naphthalene cation. In both cases, charge transfer reactions have been primarily used because of their universality. Finally, a state-of-the-art of the TPI-CM technique using the CERISES mass spectrometer is given, indicating current limitations as well as prospects of improvement.

Résumé: Context. Cold cores are one of the first steps of star formation, characterized by densities of a few 104–105 cm−3, low temperatures (15 K and below), and very low external UV radiation. In these dense environments, a rich chemistry takes place on the surfaces of dust grains. Understanding the physico-chemical processes at play in these environments is essential to tracing the origin of molecules that are predominantly formed via reactions on dust grain surfaces. Aims. We observed the cold core LDN 429-C (hereafter L429-C) with the NOEMA interferometer and the IRAM 30 m single dish telescope in order to obtain the gas-phase abundances of key species, including CO and CH3OH. Comparing the data for methanol to the methanol ice abundance previously observed with Spitzer allows us to put quantitative constraints on the efficiency of the non-thermal desorption of this species. Methods. With physical parameters determined from available Herschel data, we computed abundance maps of 11 detected molecules with a non-local thermal equilibrium (LTE) radiative transfer model. These observations allowed us to probe the molecular abundances as a function of density (ranging from a few 103 to a few 106 cm−3) and visual extinction (ranging from 7 to over 75), with the variation in temperature being restrained between 12 and 18 K. We then compared the observed abundances to the predictions of the Nautilus astrochemical model. Results. We find that all molecules have lower abundances at high densities and visual extinctions with respect to lower density regions, except for methanol, whose abundance remains around 4.5 × 10−10 with respect to H2. The CO abundance spreads over a factor of 10 (from an abundance of 10−4 with respect to H2 at low density to 1.8 × 10−5 at high density) while the CS, SO, and H2S abundances vary by several orders of magnitude. No conclusion can be drawn for CCS, HC3N, and CN because of the lack of detections at low densities. Comparing these observations with a grid of chemical models based on the local physical conditions, we were able to reproduce these observations, allowing only the parameter time to vary. Higher density regions require shorter times than lower density regions. This result can provide insights on the timescale of the dynamical evolution of this region. The increase in density up to a few 104 cm−3 may have taken approximately 105 yr, while the increase to 106 cm−3 occurs over a much shorter time span (104 yr). Comparing the observed gas-phase abundance of methanol with previous measurements of the methanol ice, we estimate a non-thermal desorption efficiency between 0.002 and 0.09%, increasing with density. The apparent increase in the desorption efficiency cannot be reproduced by our model unless the yield of cosmic-ray sputtering is altered due to the ice composition varying as a function of density.