Photodissociation of HCN and HNC isomers in the 7-10 eV energy range

13 págs.; 11 figs.; 1 tab.The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereafter electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation. ©2016 AIP Publishing LLCThe research leading to these results has received funding from the European Research Council (ERC Grant No. 610256: NANOCOSMOS) and the Spanish Ministerio de Economía y Competividad under Grant Nos. CSD2009-00038, AYA2009-07304, AYA2012-32032, and FIS2014-52172-C2.Peer Reviewe

Estudio de la Química en la Envoltura Circunestelar IRC+10216

Tesis doctoral inédita. Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física Teórica . Fecha de lectura: 28-06-200

Discovery of five cyano derivatives of propene with the QUIJOTE line survey

We report the discovery of five cyano derivatives of propene towards TMC-1 with the QUIJOTE line survey: $trans$ and $cis$-crotononitrile ($t$-CH$_3$CHCHCN, $c$-CH$_3$CHCHCN), methacrylonitrile (CH$_2$C(CH$_3$)CN), and $gauche$ and $cis$-allyl cyanide ($g$-CH$_2$CHCH$_2$CN and $c$-CH$_2$CHCH$_2$CN). The observed transitions allowed us to derive a common rotational temperature of 7$\pm$1 K for all them. The derived column densities are N($t$-CH$_3$CHCHCN)=(5$\pm$0.5)$\times$10$^{10}$ cm$^{-2}$, N($c$-CH$_3$CHCHCN)=(1.3$\pm$0.2)$\times$10$^{11}$ cm$^{-2}$, N(CH$_2$C(CH$_3$)CN)=(1.0$\pm$0.1)$\times$10$^{11}$ cm$^{-2}$, N($g$-CH$_2$CHCH$_2$CN)=(8.0$\pm$0.8)$\times$10$^{10}$ cm$^{-2}$, and N($c$-CH$_2$CHCH$_2$CN)=(7.0$\pm$0.7)$\times$10$^{10}$ cm$^{-2}$, respectively. The abundance of cyano-propene relative to that of propene is thus $\sim$10$^{-2}$, which is considerably lower than those of other cyano derivatives of abundant hydrocarbons. Upper limits are obtained for two ethynyl derivatives of propene ($E$ and $Z$-CH$_3$CHCHCCH).Comment: Accepted for publication in Astronomy and Astrophysics Letter

Discovery of Interstellar Propylene (CH_2CHCH_3): Missing Links in Interstellar Gas-Phase Chemistry

We report the discovery of propylene (also called propene, CH_2CHCH_3) with the IRAM 30-m radio telescope toward the dark cloud TMC-1. Propylene is the most saturated hydrocarbon ever detected in space through radio astronomical techniques. In spite of its weak dipole moment, 6 doublets (A and E species) plus another line from the A species have been observed with main beam temperatures above 20 mK. The derived total column density of propylene is 4 10^13 cm^-2, which corresponds to an abundance relative to H_2 of 4 10^-9, i.e., comparable to that of other well known and abundant hydrocarbons in this cloud, such as c-C_3H_2. Although this isomer of C_3H_6 could play an important role in interstellar chemistry, it has been ignored by previous chemical models of dark clouds as there seems to be no obvious formation pathway in gas phase. The discovery of this species in a dark cloud indicates that a thorough analysis of the completeness of gas phase chemistry has to be done.Comment: 13 pages, 2 figures, accepted for publication in ApJ

Discovery of two new interstellar molecules with QUIJOTE: HCCCHCCC and HCCCCS

We report on the discovery of two new molecules, HCCCHCCC and HCCCCS, towards the starless core TMC-1 in the Taurus region from the QUIJOTE line survey in the 31.1-50.2 GHz frequency range. We identify a total of twenty-nine lines of HCCCHCCC and six rotational transitions of HCCCCS. The rotational quantum numbers range from Ju=10 up to 15 and Ka <=2 for HCCCHCCC and Ju=21/2 up to 31/2 for HCCCCS. We derived a column density for HCCCHCCC of N=(1.3+/-0.2)x10^11 cm-2 with a rotational temperature of 6+/-1 K, while for HCCCCS we derived N=(9.5+/-0.8)x10^10 cm-2 and Trot =10+/-1 K. The abundance of HCCCHCCC is higher than that of its recently discovered isomer, l-H2C6. If we compare HCCCCS with its related molecules, HCS and HCCS, we obtain abundance ratios HCS/HCCCCS=58 and HCCS/HCCCCS=7.2. We investigated the formation of these two molecules using chemical modelling calculations. The observed abundances can be accounted for by assuming standard gas-phase formation routes involving neutral-neutral reactions and ion-neutral reactions.Comment: arXiv admin note: text overlap with arXiv:2206.0899

Detection of C3O in IRC+10216: Oxygen-Carbon chain chemistry in the outer envelope

The oxygen-bearing species C3O has been identified in the circumstellar envelope of the carbon star IRC +10216. The J = 8-->7, 9-->8, 10-->9, 14-->13, and 15-->14 transitions were detected at 2 and 3 mm using the Arizona Radio Observatory’s 12 m telescope. Measurements of the J = 9-->8, 10-->9, and 12-->11 lines were simultaneously conducted at the IRAM 30 m telescope. The line profiles of C3O are roughly U-shaped, indicating an extended shell distribution for this molecule in IRC +10216. The total column density derived for C3O is 1.2x10^12 cm^-2, at least an order of magnitude higher than that predicted by current chemical models. However, a revised model that includes reactions of atomic oxygen with carbon-chain radicals, such as l-C3H and C4, can reproduce the observed abundance. This model also predicts that C3O arises from a shell source with an outer radius near r ∼ 30", consistent with the observations. These results suggest that gas phase neutral-neutral chemistry may be producing the oxygen-bearing molecules present in the outer envelope of IRC +10216.This material is based on work supported by the National Aeronautics and Space Administration through the NASA Astrobiology Institute under Cooperative Agreement CAN-02-OSS-02 issued through the Office of Space Science. We also acknowledge support from Spanish MEC under project AYA2003-2785 and from "Comunidad de Madrid" under PRICIT project S-0505/ESP-0237 (ASTROCAM). E. D. T. thanks NSF for a graduate research fellowship, and M. A. acknowledges Spanish MEC for a predoctoral grant AP2003-4619.Peer reviewe

The magnesium paradigm in IRC+10216: Discovery of MgC4_4H+^+, MgC3_3N+^+, MgC6_6H+^+, and MgC5_5N+^+

We found four series of harmonically related lines in IRC\,+10216 with the Yebes\,40m and IRAM\,30m telescopes. The first series corresponds to a molecule with a rotational constant, $B$, of 1448.5994$\pm$0.0013 MHz and a distortion constant, $D$, of 63.45$\pm$1.15 Hz and covers upper quantum numbers from $J_u$=11 up to 33 (B1449). The second series is fitted with $B$=1446.9380$\pm$0.0098 MHz and $D$=91$\pm$23 Hz and covers upper quantum numbers from $J_u$=11 up to 17 (B1447). The third series is fitted with $B$=598.7495$\pm$0.0011 MHz and D=6.13$\pm$0.43 Hz and covers quantum numbers from $J_u$=26 up to 41 (B599). Finally, the frequencies of the last series of lines can be reproduced with $B$=594.3176$\pm$0.0026 MHz and $D$=4.92$\pm$1.16 Hz (B594). The large values of $D$ point toward four metal-bearing carriers. After exploring all plausible candidates containing Na, Al, Mg, and other metals, our ab initio calculations indicate that the cations MgC$_4$H$^+$, MgC$_3$N$^+$, MgC$_6$H$^+$, and MgC$_5$N$^+$ must be the carriers of B1449, B1447, B599, and B594, respectively. These cations could be formed by the radiative association of Mg$^+$ with C$_4$H, C$_3$N, C$_6$H, and C$_5$N, respectively. We calculated the radiative association rate coefficient of Mg$^+$ with C$_4$H, C$_3$N, C$_6$H, and C$_5$N and incorporated them in our chemical model. The results confirm that the Mg-bearing cations can be formed through these radiative association reactions in the outer layers of IRC\,+10216. This is the first time that cationic metal-bearing species have been found in space. These results provide a new paradigm on the reactivity of ionized metals with abundant radicals and open the door for further characterization of similar species in metal-rich astrophysical environments

Astronomical identification of CN-, the smallest observed molecular anion

We present the first astronomical detection of a diatomic negative ion, the cyanide anion CN-, as well as quantum mechanical calculations of the excitation of this anion through collisions with para-H2. CN- is identified through the observation of the J = 2-1 and J = 3-2 rotational transitions in the C-star envelope IRC +10216 with the IRAM 30-m telescope. The U-shaped line profiles indicate that CN-, like the large anion C6H-, is formed in the outer regions of the envelope. Chemical and excitation model calculations suggest that this species forms from the reaction of large carbon anions with N atoms, rather than from the radiative attachment of an electron to CN, as is the case for large molecular anions. The unexpectedly large abundance derived for CN-, 0.25 % relative to CN, makes likely its detection in other astronomical sources. A parallel search for the small anion C2H- remains so far unconclusive, despite the previous tentative identification of the J = 1-0 rotational transition. The abundance of C2H- in IRC +10216 is found to be vanishingly small, < 0.0014 % relative to C2H.Comment: 5 pages, 4 figures; accepted for publication in A&A Letter

Laboratory and astronomical discovery of the cyanovinyl radical H2CCCN

We report the first laboratory and interstellar detection of the alpha-cyano vinyl radical (H2CCCN). This species was produced in the laboratory by an electric discharge of a gas mixture of vinyl cyanide, CH2CHCN, and Ne, and its rotational spectrum was characterized using a Balle-Flygare narrowband-type Fourier-transform microwave spectrometer operating in the frequency region of 8-40 GHz. The observed spectrum shows a complex structure due to tunneling splittings between two torsional sublevels of the ground vibronic state, 0+ and 0-, derived from a large-amplitude inversion motion. In addition, the presence of two equivalent hydrogen nuclei makes necessary to discern between ortho- and para-H2CCCN. A least squares analysis reproduces the observed transition frequencies with a standard deviation of ca. 3 kHz. Using the laboratory predictions, this radical is detected in the cold dark cloud TMC-1 using the Yebes 40m telescope and the QUIJOTE line survey. The 404-303 and 505-404 rotational transitions, composed of several hyperfine components, were observed in the 31.0-50.4 GHz range. Adopting a rotational temperature of 6K we derive a column density of (1.4+/-0.2)e11 cm-2 and (1.1+/-0.2)e11 cm-2 for ortho-H2CCCN and para-H2CCCN, respectively. The reactions C + CH3CN, and perhaps also N + CH2CCH, emerge as the most likely routes to H2CCCN in TMC-1.Comment: Accepted for publication in A&A Letters on 18/07/202

Ultra-deep 31.0-50.3 GHz spectral survey of IRC+10216

51 pags., 43 figs., 3 tabs.Context. The carbon-rich envelope of the asymptotic giant branch star CW Leo, IRC+10216, is one of the richest molecular sources in the sky. Available spectral surveys below 51 GHz are more than 25 years old, and new work is needed. Aims. Characterizing the rich molecular content of this source, specially for heavy species, requires carrying out very sensitive spectral surveys at low frequencies. In particular, we have achieved an rms in the range 0.2-0.6mK per MHz. Methods. Long Q band (31.0-50.3 GHz) single-dish integrations were carried out with the Yebes-40m telescope using specifically built receivers. The most recent line catalogs were used to identify the lines. Results. The data contain 652 spectral features, corresponding to 713 transitions from 81 species (we count the isomers, isotopologs, and ortho/para species separately). Only 57 unidentified lines remain with signal-to-noise ratios ≤3. Some new species and/or vibrational modes have been discovered for the first time with this survey. Conclusions. This IRC+10216 spectral survey is by far the most sensitive survey carried out to date in the Q band. It therefore provides the most complete view of IRC+10216 from 31.0 to 50.3 GHz, giving unique information about its molecular content, especially for heavy species. Rotational diagrams built from the data provide valuable information about the physical conditions and chemical content of this circumstellar envelope.We thank Ministerio de Ciencia e Innovación of Spain for funding support through projects PID2019-106110GB-I00, PID2019- 107115GB-C21/AEI/10.13039/501100011033, PID2019-106235GB-I00, and grant FJCI-2016-27983 for CB. We also thank ERC for funding through grant ERC-2013-Syg-610256-NANOCOSMOS. M.A. thanks MICIU for grant RyC2014-16277