Twisted Intramolecular Charge Transfer in Protonated Amino Pyridine

International audienceThe excited state properties of protonated ortho (2-), meta (3-) and para (4-) aminopyridine molecules have been investigated through UV photo fragmentation spectroscopy and excited state couple cluster CC2 calculations. Cryogenic ion spectroscopy allows recording well-resolved vibronic spectroscopy that can be nicely reproduced through Franck Condon simulations of the pp* local minimum of the excited state potential energy surface. The excited state lifetimes have also been measured through a pump-probe excitation scheme and compared to the estimated radiative lifetimes. Although protonated aminopyridines are rather simple aromatic molecules, their deactivation mechanisms are indeed quite complex with unexpected results. In protonated 3-and 4-aminopyridine, the fragmentation yield is negligible around the band origin, which implies the absence of internal conversion to the ground state. Besides, a twisted intramolecular charge transfer reaction is evidenced in protonated 4-aminopyridine around the band origin, while excited state proton transfer from the pyridinic nitrogen to the adjacent carbon atom opens with roughly 500 cm-1 of excess energy

Chiral molecule formation in interstellar ice analogs: alpha-aminoethanol NH 2 CH(CH 3 )OH

International audienceAims. Aminoalcohol molecules such as alpha-aminoethanol NH 2 CH(CH 3)OH may be aminoacid precursors. We attempt to charac-terize and detect this kind of molecules which is important to establish a possible link between interstellar molecules and life as we know it on Earth. Methods. We use Fourier transform infrared (FTIR) spectroscopy and mass spectrometry to study the formation of alpha-aminoethanol NH 2 CH(CH 3)OH in H 2 O:NH 3 : CH 3 CHO ice mixtures. Isotopic substitution with 15 NH 3 and ab-initio calculation are used to confirm the identification of alpha-aminoethanol. Results. After investigating the thermal reaction of solid NH 3 and acetaldehyde CH 3 CHO at low temperature, we find that this reac-tion leads to the formation of a chiral molecule, the alpha aminoethanol NH 2 CH(CH 3)OH. For the first time, we report the infrared and mass spectra of this molecule. We also report on its photochemical behavior under VUV irradiation. We find that the main photo-product is acetamide (NH 2 COCH 3). Data provided in this work indicates that alpha-aminoethanol is formed in one hour at 120 K and suggests that its formation in warm interstellar environments such as protostellar envelopes or cometary environments is likely

Hydrogenation of solid hydrogen cyanide HCN and methanimine CH2NH at low temperature

International audienceContext. Hydrogenation reactions dominate grain surface chemistry in dense molecular clouds and lead to the formation of complex saturated molecules in the interstellar medium. Aims. We investigate in the laboratory the hydrogenation reaction network of hydrogen cyanide HCN. Methods. Pure hydrogen cyanide HCN and methanimine CH2NH ices are bombarded at room temperature by H-atoms in an ultra-high vacuum experiment. Warm H-atoms are generated in an H2 plasma source. The ices are monitored with Fourier-transform infrared spectroscopy in reflection absorption mode. The hydrogenation products are detected in the gas phase by mass spectroscopy during temperature-programmed desorption experiments. Results. HCN hydrogenation leads to the formation of methylamine CH3NH2, and CH2NH hydrogenation leads to the formation of methylamine CH3NH2, suggesting that CH2NH can be a hydrogenation-intermediate species between HCN and CH3NH2. Conclusions. In cold environments the HCN hydrogenation reaction can produce CH3NH2, which is known to be a glycine precursor, and to destroy solid-state HCN, preventing its observation in molecular clouds ices

Experimental investigation of aminoacetonitrile formation through the Strecker synthesis in astrophysical-like conditions: reactivity of methanimine (CH2NH), ammonia (NH3), and hydrogen cyanide (HCN)

International audienceAstronomy & Astrophysics Experimental investigation of aminoacetonitrile formation through the Strecker synthesis in astrophysical-like conditions: reactivity of methanimine (CH 2 NH), ammonia (NH 3), and hydrogen cyanide (HCN) ABSTRACT Context. Studing chemical reactivity in astrophysical environments is an important means for improving our understanding of the origin of the organic matter in molecular clouds, in protoplanetary disks, and possibly, as a final destination, in our solar system. Laboratory simulations of the reactivity of ice analogs provide important insight into the reactivity in these environments. Here, we use these experimental simulations to investigate the Strecker synthesis leading to the formation of aminoacetonitrile in astrophysical-like conditions. The aminoacetonitrile is an interesting compound because it was detected in SgrB2, hence could be a precursor of the smallest amino acid molecule, glycine, in astrophysical environments. Aims. We present the first experimental investigation of the formation of aminoacetonitrile NH 2 CH 2 CN from the thermal processing of ices including methanimine (CH 2 NH), ammonia (NH 3), and hydrogen cyanide (HCN) in interstellar-like conditions without VUV photons or particules. Methods. We use Fourier Transform InfraRed (FTIR) spectroscopy to monitor the ice evolution during its warming. Infrared spec-troscopy and mass spectroscopy are then used to identify the aminoacetonitrile formation. Results. We demonstrate that methanimine can react with − CN during the warming of ice analogs containing at 20 K methanimine, ammonia, and [NH + 4 − CN] salt. During the ice warming, this reaction leads to the formation of poly(methylene-imine) polymers. The polymer length depend on the initial ratio of mass contained in methanimine to that in the [NH + 4 − CN] salt. In a methanimine excess, long polymers are formed. As the methanimine is progressively diluted in the [NH + 4 − CN] salt, the polymer length decreases until the aminoacetonitrile formation at 135 K. Therefore, these results demonstrate that aminoacetonitrile can be formed through the second step of the Strecker synthesis in astrophysical-like conditions

Chemical complexity in protoplanetary disks in the era of ALMA and Rosetta

Comets provide a unique insight into the molecular composition and complexity of the material in the primordial solar nebula. Recent results from the Rosetta mission, currently monitoring comet 67P/Churyumov-Gerasimenko in situ, and ALMA (the Atacama Large Millimeter/submillimeter Array) have demonstrated a tantalising link between the chemical complexity now confirmed in disks (via the detection of gas-phase cf.CH3CN Öberg et al. [13]) and that confirmed on the surface of 67P (Goesmann et al. [3]), raising questions concerning the chemical origin of such species (cloud or inheritance versus disk synthesis). Results from an astrochemical model of a protoplanetary disk are presented in which complex chemistry is included and in which it is assumed that simple ices only are inherited from the parent molecular cloud. The model results show good agreement with the abundances of several COMs observed on the surface of 67P with Philae/COSAC. Cosmic-ray and X-ray-induced photoprocessing of predominantly simple ices inherited by the protoplanetary disk is sufficient to generate a chemical complexity similar to that observed in comets. This indicates that the icy COMs detected on the surface of 67P may have a disk origin. The results also show that gas-phase cf.CH3CN is abundant in the inner warm disk atmosphere where hot gas-phase chemistry dominates and potentially erases the ice chemical signature. Hence, cf.CH3CN may not be an unambiguous tracer of the complex organic ice reservoir. However, a better understanding of the hot gas-phase chemistry of cf.CH3CN is needed to confirm this preliminary conclusion

Broadband spectroscopy of astrophysical ice analogues: II. Optical constants of CO and CO2_2 ices in the terahertz and infrared ranges

Context: Broadband optical constants of astrophysical ice analogues in the infrared (IR) and terahertz (THz) ranges are required for modeling the dust continuum emission and radiative transfer in dense and cold regions, where thick icy mantles are formed on the surface of dust grains. Aims: In this paper, the THz time-domain spectroscopy (TDS) and the Fourier-transform IR spectroscopy (FTIR) are combined to study optical constants of CO and CO$_2$ ices in the broad THz-IR spectral range. Methods: The measured ices are grown at cryogenic temperatures by gas deposition on a cold Si window. A method to quantify the broadband THz-IR optical constants of ices is developed based on the direct reconstruction of the complex refractive index of ices in the THz range from the TDS data, and the use of the Kramers-Kronig relation in the IR range for the reconstruction from the FTIR data. Uncertainties of the Kramers-Kronig relation are eliminated by merging the THz and IR spectra. The reconstructed THz-IR response is then analyzed using classical models of complex dielectric permittivity. Results: The complex refractive index of CO and CO$_2$ ices deposited at the temperature of $28$ K is obtained in the range of 0.3--12.0 THz. Based on the measured dielectric constants, opacities of the astrophysical dust with CO and CO$_2$ icy mantles are computed. Conclusions: The developed method can be used for a model-independent reconstruction of optical constants of various astrophysical ice analogs in a broad THz-IR range. Such data can provide important benchmarks to interpret the broadband observations from the existing and future ground-based facilities and space telescopes. The reported results will be useful to model sources that show a drastic molecular freeze-out, such as central regions of prestellar cores and mid-planes of protoplanetary disks, as well as CO and CO$_2$ snow lines in disks.Comment: Accepted for publication in A&A, 9 pages, 7 figure

Identification of Large Equivalent Width Dusty Galaxies at 4 << z << 6 from Sub-mm Colours

Infrared (IR), sub-millimetre (sub-mm) and millimetre (mm) databases contain a huge quantity of high quality data. However, a large part of these data are photometric, and are thought not to be useful to derive a quantitative information on the nebular emission of galaxies. The aim of this project is first to identify galaxies at z > 4-6, and in the epoch of reionization from their sub-mm colours. We also aim at showing that the colours can be used to try and derive physical constraints from photometric bands, when accounting for the contribution from the IR fine structure lines to these photometric bands. We model the flux of IR fine structure lines with CLOUDY, and add them to the dust continuum emission with CIGALE. Including or not emission lines in the simulated spectral energy distribution (SED) modifies the broad band emission and colours. The introduction of the lines allows to identify strong star forming galaxies at z > 4 - 6 from the log10 (PSW_250um/PMW_350um) versus log10 (LABOCA_870um/PLW_500um) colour-colour diagramme. By comparing the relevant models to each observed galaxy colour, we are able to roughly estimate the fluxes of the lines, and the associated nebular parameters. This method allows to identify a double sequence in a plot built from the ionization parameter and the gas metallicity. The HII and photodissociation region (PDR) fine structure lines are an essential part of the SEDs. It is important to add them when modelling the spectra, especially at z > 4 - 6 where their equivalent widths can be large. Conversely, we show that we can extract some information on strong IR fine structure lines and on the physical parameters related to the nebular emission from IR colour-colour diagrams.Comment: Paper accepted in Astronomy and Astrophysics on 10 November 202