Lucie Kolesniková

A rigorous detection of interstellar CH3NCO: An important missing species in astrochemical networks

The recent analysis of the composition of the frozen surface of comet 67P/Churyumov-Gerasimenko has revealed a significant number of complex organic molecules. Methyl isocyanate (CH3NCO) is one of the more abundant species detected on the comet surface. In this work we report extensive characterization of its rotational spectrum resulting in a list of 1269 confidently assigned laboratory lines and its detection in space towards the Orion clouds where 399 lines of the molecule have been unambiguously identified. We find that the limited mm-wave laboratory data reported prior to our work require some revision. The abundance of CH3NCO in Orion is only a factor of ten below those of HNCO and CH3CN. Unlike the molecular abundances in the coma of comets, which correlate with those of warm molecular clouds, molecular abundances in the gas phase in Orion are only weakly correlated with those measured on the comet surface. We also compare our abundances with those derived recently for this molecule towards Sgr B2 (Halfen et al. 2015). A more accurate abundance of CH3NCO is provided for this cloud based on our extensive laboratory work.

Searching for Trans Ethyl Methyl Ether in Orion KL

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm-2 and ≤(1.0 ± 0.2)× 1015 cm-2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion.

Detailed study of fine and hyperfine structures in rotational spectra of the free fluoroformyloxyl radical FCO2

More than 160 new hyperfine components of rotational transitions of the free fluoroformyloxyl radical FCO(2) have been measured using the Prague millimeter wave high resolution spectrometer. The frequencies of these transitions together with the previously measured data were analyzed in detail and precise values of magnetic hyperfine and fine parameters were obtained. These new parameters significantly improve the values of previously determined hyperfine parameters which were rather unreliable. The new fine and hyperfine parameters obtained in this study are compatible with those of the simultaneously electron paramagnetic resonance study. Besides that, significantly improved ground state rotational and centrifugal distortion constants of the fluoroformyloxyl radical were derived.

Comprehensive Analysis of Prebiotic Propenal up to 660 GHz

Since interstellar detection of propenal is only based on two rotational transitions in the centimeter wave region, its high resolution rotational spectrum has been measured up to 660 GHz and fully characterized by assignment of more than 12,000 transitions to provide direct laboratory data to the astronomical community. Spectral assignments and analysis include transitions from the ground state of the trans and cis isomers, three trans-13C isotopologues, and ten excited vibrational states of the trans form. Combining new millimeter and submillimeter data with those from the far-infrared region has yielded the most precise set of spectroscopic constants of trans-propenal obtained to date. Newly determined rotational constants, centrifugal distortion constants, vibrational energies, and Coriolis and Fermi interaction constants are given with high accuracy and were used to predict transition frequencies and intensities over a wide frequency range. Results of this work should facilitate astronomers further observation of propenal in the interstellar medium.

The fluoroformyloxyl radical geometry and ground-state rotational spectra of the free FC18O2· radical.

The rotational spectra of the isotopically substituted free fluoroformyloxyl radical FC(18)O(2·) were measured using the Prague millimeter-wave high-resolution spectrometer. More than 110 rotational-fine-hyperfine transition lines were observed and assigned to appropriate quantum numbers in the frequency range of 235-270 GHz. The obtained transition frequencies were analyzed with standard effective Hamiltonians to acquire a set of precise rotational, centrifugal-distortion, fine, and hyperfine structure molecular constants. Merging the new FC(18)O(2·) isotopologue molecular parameters with those previously obtained for the ordinary FC(16)O(2)[middle dot] radical, the substitution molecular geometry in the ground vibronic state was evaluated. The molecular parameters for both radical isotopologues were also calculated by several quantum chemistry methods and their calculated mutual ratios are in remarkable agreement with the experimental FC(16)O(2·)/FC(18)O(2·) parameter ratios. The measurements, assignments of the 18-oxygen isotopologue FC(18)O(2·) radical millimeter-wave transitions, as well as the derivation of the fluoroformyloxyl radical ground-state geometry have been carried out for the first time.

Geometry and Microwave Rotational Spectrum of the FC16O18O• Radical

The rotational spectrum of an asymmetrically substituted isotopologue of the fluoroformyloxyl radical FC(16)O(18)O(•) with resolved fine and hyperfine structures were measured and analyzed for the very first time. The molecular parameters of this radical obtained from the spectral analysis were processed along with the symmetrical isotopologues FC(16)O2(•) and FC(18)O2(•) and accurate substitution geometry was attained. In addition to those, coupled cluster quantum chemistry calculations were used to scale the experimental parameters, and in this manner, trustworthy values of the equilibrium and ground state geometries were derived.

Millimeter wave spectra of ethyl isocyanate and searches for it in Orion KL and Sagittarius B2

Context Relatively high abundances of methyl isocyanate (CH3NCO), a methyl derivative of isocyanic acid (HNCO), found in the Orion KL and Sgr B2 molecular clouds suggest that its ethyl derivative, ethyl isocyanate (CH3CH2NCO), may also be present. Aims The aim of this work is to provide accurate experimental frequencies of ethyl isocyanate in its ground and excited vibrational states in the millimeter wave region to support searches for it in the interstellar medium. Methods The rotational spectrum of ethyl isocyanate was recorded at room temperature from 80 to 340 GHz using the millimeter wave spectrometer in Valladolid. Assigned rotational transitions were analyzed using the S -reduced semirigid-rotor Hamiltonian. Results More than 1100 distinct frequency lines were analyzed for the ground vibrational state of the cis conformer as well as for three vibrational satellites corresponding to successive excitation of the lowest-energy C-N torsional mode. Newly determined rotational and centrifugal distortion constants were used for searches of spectral features of ethyl isocyanate in Orion KL and Sgr B2 clouds. Upper limits to CH3CH2NCO in these high-mass star-forming regions were obtained.

Laboratory rotational spectrum and astronomical search for methoxyacetaldehyde

Context Methoxyacetaldehyde belongs to a group of structural isomers with the general formula C3H6O2, of which methyl acetate and ethyl formate are known interstellar molecules. Rotational data available for methoxyacetaldehyde are limited to 40 GHz, which makes predictions at higher frequencies rather uncertain. Aims The aim of this work is to provide accurate experimental frequencies of methoxyacetaldehyde in the millimeter-wave region to support its detection in the interstellar medium. Methods The rotational spectrum of methoxyacetaldehyde was recorded at room-temperature from 75 to 120 GHz and from 170 to 310 GHz using the millimeter-wave spectrometer in Valladolid. Additional measurements were also performed at conditions of supersonic expansion from 6 to 18 GHz. The assigned rotational transitions were analyzed using the S -reduced semirigid-rotor Hamiltonian. Results We newly assigned over 1000 lines for the most stable conformer of methoxyacetaldehyde in its ground state and five lowest excited vibrational states, and precise sets of spectroscopic constants were obtained. We searched for spectral features of methoxyacetaldehyde in the high-mass star-forming regions Orion KL and Sagittarius B2, as well as in the cold dark cloud Barnard 1 (B1-b). No lines belonging to methoxyacetaldehyde were detected above the detection limit of our data. We provide upper limits to the methoxyacetaldehyde colum density in these sources.

Rotational spectrum of methoxyamine up to 480 GHz: a laboratory study and astronomical search

Aims Methoxyamine is a potential interstellar amine that has been predicted by gas-grain chemical models for the formation of complex molecules. The aim of this work is to provide direct experimental frequencies of its ground-vibrational state in the millimeter- and submillimeter-wave regions to achieve its detection in the interstellar medium. Methods Methoxyamine was chemically liberated from its hydrochloride salt, and its rotational spectrum was recorded at room temperature from 75 to 480 GHz using the millimeter-wave spectrometer in Valladolid. Many observed transitions revealed A-E splitting caused by the internal rotation of the methyl group, which had to be treated with specific internal rotation codes. Results Over 400 lines were newly assigned for the most stable conformer of methoxyamine, and a precise set of spectroscopic constants was obtained. Spectral features of methoxyamine were then searched for in the Orion KL, Sgr B2, B1-b, and TMC-1 molecular clouds. Upper limits to the column density of methoxyamine were derived.

Laser ablated hydantoin: A high resolution rotational study

Laser ablation techniques coupled with broadband and narrowband Fourier transform microwave spectroscopies have allowed the high resolution rotational study of solid hydantoin, an important target in astrochemistry as a possible precursor of glycine. The complicated hyperfine structure arising from the presence of two 14N nuclei in non-equivalent positions has been resolved and interpreted in terms of the nuclear quadrupole coupling interactions. The results reported in this work provide a solid base for the interstellar searches of hydantoin in the astrophysical surveys. The values of the nuclear quadrupole coupling constants have been also discussed in terms of the electronic environment around the respective nitrogen atom.