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P. de Vicente

Publications and source records attributed to P. de Vicente.

At least 55 records · Page 3Linked to original sources

Discovery of the elusive thioketenylium, HCCS+, in TMC-1

We report the detection in TMC-1 of the cation HCCS+ (3Sigma-), which is the protonated form of the widespread radical CCS. This is the first time that a protonated radical has been detected in a cold dark cloud. Twenty-six hyperfine components from twelve rotational transitions have been observed with the Yebes 40m and IRAM 30m radio telescopes. We confidently assign the characteristic rotational spectrum pattern to HCCS+ based on the good agreement between the astronomical and theoretical spectroscopic parameters. The column density of HCCS+ is (1.1+/-0.1)e12 cm-2, and the CCS/HCCS+ abundance ratio is 50+/-10, which is very similar to that of CS/HCS+ (35+/-8) and CCCS/HCCCS+ (65+/-20). From a state-of-the-art gas-phase chemical model, we conclude that HCCS+ is mostly formed by reactions of proton transfer from abundant cations such as HCO+, H3O+, and H3+ to the radical CCS.

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New deuterated species in TMC-1: Detection of CH2DC4H with the QUIJOTE line survey

We report the first detection in space of the single deuterated isotopologue of methyldiacetylene, CH2DC4H. A total of 12 rotational transitions, with J = 8-12 and Ka = 0 and 1, were identified for this species in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. The observed frequencies allowed us to obtain, for the first time, the spectroscopic parameters of this deuterated isotopologue. We derived a column density of (5.5+/-0.2)e11 cm-2. The abundance ratio between CH3C4H and CH2DC4H is 24+/-2. This ratio is similar to that found for the CH3C3N/CH2DC3N analogue system, which is 22+/-2.We did not detect the deuterated species CH3C4D, which has already been observed in laboratory experiments. The detection of deuterated CH3C4H allows us to extend the discussion on the chemical mechanisms of deuterium fractionation at work in TMC-1 using a new gas-phase chemical model with multiply deuterated molecules. Introducing a possible deuterium exchange reaction between CH3CCH and atomic deuterium allows us to account for the CH3C4H/CH2DC4H abundance ratio.

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Detection of the propargyl radical at lambda 3 mm

We report the detection of the propargyl radical (CH2CCH) in the cold dark cloud TMC-1 in the lambda 3 mm wavelength band. We recently discovered this species in space toward the same source at a wavelength of lambda 8 mm. In those observations, various hyperfine components of the 2,0,2-1,0,1 rotational transition, at 37.5 GHz, were detected using the Yebes 40m telescope. Here, we used the IRAM 30m telescope to detect ten hyperfine components of the 5,0,5-4,0,4 rotational transition, lying at 93.6 GHz. The observed frequencies differ by 0.2 MHz with respect to the predictions from available laboratory data. This difference is significant for a radioastronomical search for CH2CCH in interstellar sources with narrow lines. We thus included the measured frequencies in a new spectroscopic analysis to provide accurate frequency predictions for the interstellar search for propargyl at mm wavelengths. Moreover, we recommend that future searches for CH2CCH in cold interstellar clouds are carried out at lambda 3 mm, rather than at lambda 8 mm. The 5,0,5-4,0,4 transition is about five times more intense than the 2,0,2-1,0,1 one in TMC-1, which implies that detecting the former requires about seven times less telescope time than detecting the latter. We constrain the rotational temperature of CH2CCH in TMC-1 to 9.9 +/- 1.5 K, which indicates that the rotational levels of this species are thermalized at the gas kinetic temperature. The revised value of the column density of CH2CCH (including ortho and para species) is (1.0 +/- 0.2)e14 cm-2, and thus the CH2CCH/CH3CCH abundance ratio is revised from slightly below one to nearly one. This study opens the door for future detections of CH2CCH in other cold interstellar clouds, making possible to further investigate the role of this very abundant hydrocarbon radical in the synthesis of large organic molecules such as aromatic rings.

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Discovery of HCCCO and C5O in TMC-1 with the QUIJOTE line survey

We report on the detection, for the first time in space, of the radical HCCCO and of pentacarbon monoxide, C5O. The derived column densities are (1.6+/-0.2)e11 cm-2 and (1.5+/-0.2)e10 cm-2, respectively. We have also analysed the data for all the molecular species of the families HCnO and CnO within our QUIJOTE line survey. Upper limits are obtained for HC4O, HC6O, C4O, and C6O. We report a robust detection of HC5O and HC7O based on 14 and 12 rotational lines detected with a signal-to-noise ratio >30 and >5,respectively. The derived N(HC3O)/N(HC5O) abundance ratio is 0.09+/-0.03, while N(C3O)/N(C5O) is 80+/-2, and N(HC5O)/N(HC7O) is 2.2+/-0.3. As opposed to the cyanopolyyne family, HC2n+1N, which shows a continuous decrease in the abundances with increasing n, the CnO and HCnO species show a clear abundance maximum for n=3 and 5, respectively. They also show an odd and even abundance alternation, with odd values of n being the most abundant, which is reminiscent of the behaviour of CnH radicals, where in that case species with even values of n are more abundant. We explored the formation of these species through two mechanisms previously proposed, which are based on radiative associations between CnHm+ ions with CO and reactions of Cn- and CnH- anions with O atoms, and we found that several species, such as C5O, HC4O, and HC6O, are significantly overestimated. Our understanding of how these species are formed is incomplete as of yet. Other routes based on neutral-neutral reactions such as those of Cn and CnH carbon chains with O, OH, or HCO, could be behind the formation of these species.

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

Context. IRC+10216, the carbon-rich envelope of the asymptotic giant branch (AGB) star CW Leo, 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 to carry out very sensitive spectral surveys at low frequencies. In particular in this work we have achieved an rms in the range 0.2-0.6 mK 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. State of the art line catalogs are used for line identification. Results. A total of 652 spectral features corresponding to 713 transitions from 81 species (we count as different the isomers, isotopologues and ortho/para species) are present in the data. 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 one carried out to this 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 on its molecular content, specially for heavy species. Rotational diagrams built from the data provide valuable information on the physical conditions and chemical content of this circumstellar envelope.

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Discovery of two isomers of ethynyl cyclopentadiene in TMC-1: Abundances of CCH and CN derivatives of hydrocarbon cycles

We report the detection of two isomers of ethynyl cyclopentadiene (c-C5H5CCH), namely 1- and 2-ethynyl-1,3-cyclopentadiene, in the direction of TMC-1. We derive column densities of (1.4 +/- 0.2)e12 cm-2, and (2.0 +/- 0.4)e12 cm-2, respectively, for these two cyclopentadiene derivatives, which imply that they are about ten times less abundant than cyclopentadiene. We also report the tentative detection of ethynyl benzene (C6H5CCH), for which we estimate a column density of (2.5 +/-0.4)e12 cm-2. We derived abundances for the corresponding cyano derivatives of cyclopentadiene and benzene and found values significantly lower than previously reported. The rotational temperature of the ethynyl and cyano derivatives of these cycles is about 9 K, that is, very close to the gas kinetic temperature of the cloud. The abundance ratio of the 1- and 2- isomers of ethynyl cyclopentadiene is 1.4 +/-0.5, while for the two isomers of cyano cyclopentadiene it is 2.4 +/- 0.6. The relative abundances of CCH over CN derivatives is 7.7 +/- 2.2 for cyclopentadiene, which probably reflects the abundance ratio of the radicals CCH and CN; this ratio is only 2.1 +/- 0.5 for benzene, which suggests that additional reactions besides cyano radicals with benzene are involved in the formation of benzonitrile. The formation of these cycles is reasonably well accounted for through a chemical scheme based on neutral-neutral reactions. It is predicted that benzene should be as abundant as cyclopentadiene in TMC-1.

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First detection of C$_2$H$_5$NCO in the ISM and search of other isocyanates towards the G+0.693-0.027 molecular cloud

Little is known about the chemistry of isocyanates (compounds with the functional group R-N=C=O) in the interstellar medium, as only four of them have been detected so far: isocyanate radical (NCO), isocyanic acid (HNCO), N-protonated isocyanic acid (H$_2$NCO$^+$) and methyl isocyanate (CH$_3$NCO). The molecular cloud G+0.693-0.027, located in the Galactic Centre, represents an excellent candidate to search for new isocyanates since it exhibits high abundances of the simplest ones, HNCO and CH$_3$NCO. After CH$_3$NCO, the next complex isocyanates are ethyl isocyanate (C$_2$H$_5$NCO) and vinyl isocyanate (C$_2$H$_3$NCO). Their detection in the ISM would enhance our understanding of the formation of these compounds in space. We have detected C$_2$H$_5$NCO and H$_2$NCO$^+$ towards G+0.693-0.027 (the former for the first time in the interstellar medium) with molecular abundances of (4.7$-$7.3)$\times$10$^{-11}$ and (1.0$-$1.5)$\times$10$^{-11}$, respectively. A ratio CH$_3$NCO / C$_2$H$_5$NCO = 8$\pm$1 is obtained; therefore the relative abundance determined for HNCO:CH$_3$NCO:C$_2$H$_5$NCO is 1:1/55:1/447, which implies a decrease by more than one order of magnitude going progressively from HNCO to CH$_3$NCO and to C$_2$H$_5$NCO. This is similar to what has been found for e.g. alcohols and thiols and suggests that C$_2$H$_5$NCO is likely formed on the surface of dust grains. In addition, we have obtained column density ratios of HNCO / NCO > 269, HNCO / H$_2$NCO$^+$ $\sim$ 2100 and C$_2$H$_3$NCO / C$_2$H$_5$NCO~<~4. A comparison of the Methyl~/~Ethyl ratios for isocyanates (-NCO), alcohols (-OH), formiates (HCOO-), nitriles (-CN) and thiols (-SH) is performed and shows that ethyl-derivatives may be formed more efficiently for the N-bearing molecules than for the O- and S-bearing molecules.

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Discovery of benzyne, o-C6H4, in TMC-1 with the QUIJOTE line survey

We report the detection, for the first time in space, of a new non-functionalised hydrocarbon cycle in the direction of TMC-1: o-C6H4 (ortho-benzyne). We derive a column density for this hydrocarbon cycle of (5 +/- 1)e11 cm-2. The abundance of this species is around 30 times lower than that of cyclopentadiene and indene. We compare the abundance of benzyne with that of other pure hydrocarbons, cycles or chains, and find that it could be formed from neutral-radical reactions such as C2H + CH2CHCCH and C + C5H5, and possibly through C4H + C2H4, C3H + CH2CCH2, and C3H2 + C3H3. Hence, the rich content of hydrocarbon cycles observed in TMC-1 could arise through a bottom-up scenario involving reactions of a few radicals with the abundant hydrocarbons recently revealed by the QUIJOTE line survey.

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Magnesium radicals MgC$_5$N and MgC$_6$H in IRC+10216

After the previous discovery of MgC$_3$N and MgC$_4$H in IRC+10216, a deeper Q-band (31.0-50.3 GHz) integration on this source had revealed two additional series of harmonically related doublets that we assigned on the basis of quantum mechanical calculations to the larger radicals MgC$_5$N and MgC$_6$H. The results presented here extend and confirm previous results on magnesium-bearing molecules in IRC\,+10216. We derived column densities of (4.7$\pm$1.3)$\times$10$^{12}$ for MgC$_5$N and (2.0$\pm$0.9)$\times$10$^{13}$ for MgC$_6$H, which imply that MgC$_5$N/MgC$_3$N=0.5 and MgC$_6$H/MgC$_4$H = 0.9. Therefore, MgC$_5$N and MgC$_6$H are present with column densities not so different from those of the immediately shorter analogs. The synthesis of these large magnesium cyanides and acetylides in IRC+10216 can be explained for their shorter counterparts by a two-step process initiated by the radiative association of Mg$^+$ with large cyanopolyynes and polyynes, which are still quite abundant in this source, followed by the dissociative recombination of the ionic complexes.

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Detection of the cyanomidyl radical (HNCN): a new interstellar species with the NCN backbone

We report here the first detection in the interstellar medium of the cyanomidyl radical (HNCN). Using the Yebes 40m and the IRAM 30m telescopes, we have targeted the doublets of the $N$=2$-$1, 4$-$3, 5$-$4, 6$-$5, and 7$-$6 transitions of HNCN toward the molecular cloud G+0.693-0.027. We have detected three unblended lines of HNCN, these are the $N$=6$-$5 doublet and one line of the $N$=4$-$3 transition. Additionally we present one line of the $N$=5$-$4 transition partially blended with emission from other species. The Local Thermodynamic Equilibrium best fit to the data gives a molecular abundance of (0.91$\pm$0.05)$\times$10$^{-10}$ with respect to H$_2$. The relatively low abundance of this species in G+0.693-0.027, and its high reactivity, suggest that HNCN is possibly produced by gas-phase chemistry. Our work shows that this highly reactive molecule is present in interstellar space, and thus it represents a plausible precursor of larger prebiotic molecules with the NCN backbone such as cyanamide (NH$_2$CN), carbodiimide (HNCNH) and formamidine (NH$_2$CHNH).

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Detection of deuterated methylcyanoacetylene, CH$_2$DC$_3$N, in TMC-1

We report the first detection in space of the single deuterated isotopologue of methylcyanoacetylene, CH$_2$DC$_3$N. A total of fifteen rotational transitions, with $J$ = 8-12 and $K_a$ = 0 and 1, were identified for this species in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. The observed frequencies were used to derive for the first time the spectroscopic parameters of this deuterated isotopologue. We derive a column density of $(8.0\pm 0.4) \times 10^{10}$ cm$^{-2}$. The abundance ratio between CH$_3$C$_3$N and CH$_2$DC$_3$N is $\sim$22. We also theoretically computed the principal spectroscopic constants of $^{13}$C isotopologues of CH$_3$C$_3$N and CH$_3$C$_4$H and those of the deuterated isotopologues of CH$_3$C$_4$H for which we could expect a similar degree of deuteration enhancement. However, we have not detected either CH$_2$DC$_4$H nor CH$_3$C$_4$D nor any $^{13}$C isotopologue. The different observed deuterium ratios in TMC-1 are reasonably accounted for by a gas phase chemical model where the low temperature conditions favor deuteron transfer through reactions with H$_2$D$^+$.

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Cumulene carbenes in TMC-1: Astronomical discovery of $l$-H$_2$C$_5$

We report the first detection in space of the cumulene carbon chain $l$-H$_2$C$_5$. A total of eleven rotational transitions, with $J_{up}$ = 7-10 and $K_a$ = 0 and 1, were detected in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. We derive a column density of (1.8$\pm$0.5)$\times$10$^{10}$ cm$^{-2}$. In addition, we report observations of other cumulene carbenes detected previously in TMC-1, to compare their abundances with the newly detected cumulene carbene chain. We find that $l$-H$_2$C$_5$ is $\sim$4.0 times less abundant than the larger cumulene carbene $l$-H$_2$C$_6$, while it is $\sim$300 and $\sim$500 times less abundant than the shorter chains $l$-H$_2$C$_3$ and $l$-H$_2$C$_4$. We discuss the most likely gas-phase chemical routes to these cumulenes in TMC-1 and stress that chemical kinetics studies able to distinguish between different isomers are needed to shed light on the chemistry of C$_n$H$_2$ isomers with $n$\,$>$\,3.

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The sulphur saga in TMC-1: Discovery of HCSCN and HCSCCH

We report the detection, for the first time in space, of cyano thioformaldehyde (HCSCN) and propynethial (HCSCCH) towards the starless core TMC-1. Cyano thioformaldehyde presents a series of prominent a- and b-type lines, which are the strongest previously unassigned features in our Q-band line survey of TMC-1. Remarkably, HCSCN is four times more abundant than cyano formaldehyde (HCOCN). On the other hand, HCSCCH is five times less abundant than propynal (HCOCCH). Surprisingly, we find an abundance ratio HCSCCH/HCSCN of 0.25, in contrast with most other ethynyl-cyanide pairs of molecules for which the CCH-bearing species is more abundant than the CN-bearing one. We discuss the formation of these molecules in terms of neutral-neutral reactions of S atoms with CH2CCH and CH2CN radicals as well as of CCH and CN radicals with H2CS. The calculated abundances for the sulphur-bearing species are, however, significantly below the observed values, which points to an underestimation of the abundance of atomic sulphur in the model or to missing formation reactions, such as ion-neutral reactions.

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Pure hydrocarbon cycles in TMC-1: Discovery of ethynyl cyclopropenylidene, cyclopentadiene and indene

We report the detection for the first time in space of three new pure hydrocarbon cycles in TMC-1: c-C3HCCH (ethynyl cyclopropenylidene), c-C5H6 (cyclopentadiene) and c-C9H8 (indene). We derive a column density of 3.1e11 cm-2 for the former cycle and similar values, in the range (1-2)e13 cm-2, for the two latter molecules. This means that cyclopentadiene and indene, in spite of their large size, are exceptionally abundant, only a factor of five less abundant than the ubiquitous cyclic hydrocarbon c-C3H2. The high abundance found for these two hydrocarbon cycles, together with the high abundance previously found for the propargyl radical (CH2CCH) and other hydrocarbons like vinyl and allenyl acetylene (Agundez et al. 2021; Cernicharo et al. 2021a,b), start to allow us to quantify the abundant content of hydrocarbon rings in cold dark clouds and to identify the intermediate species that are probably behind the in situ bottom-up synthesis of aromatic cycles in these environments. While c-C3HCCH is most likely formed through the reaction between the radical CCH and c-C3H2, the high observed abundances of cyclopentadiene and indene are difficult to explain through currently proposed chemical mechanisms. Further studies are needed to identify how are five- and six-membered rings formed under the cold conditions of clouds like TMC-1.

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O-bearing complex organic molecules at the cyanopolyyne peak of TMC-1: detection of C2H3CHO, C2H3OH, HCOOCH3, and CH3OCH3

We report the detection of the oxygen-bearing complex organic molecules propenal (C2H3CHO), vinyl alcohol (C2H3OH), methyl formate (HCOOCH3), and dimethyl ether (CH3OCH3) toward the cyanopolyyne peak of the starless core TMC-1. These molecules are detected through several emission lines in a deep Q-band line survey of TMC-1 carried out with the Yebes 40m telescope. These observations reveal that the cyanopolyyne peak of TMC-1, which is the prototype of cold dark cloud rich in carbon chains, contains also O-bearing complex organic molecules like HCOOCH3 and CH3OCH3, which have been previously seen in a handful of cold interstellar clouds. In addition, this is the first secure detection of C2H3OH in space and the first time that C2H3CHO and C2H3OH are detected in a cold environment, adding new pieces in the puzzle of complex organic molecules in cold sources. We derive column densities of (2.2 +/- 0.3)e11 cm-2, (2.5 +/- 0.5)e12 cm-2, (1.1 +/- 0.2)e12 cm-2, and (2.5 +/- 0.7)e12 cm-2 for C2H3CHO, C2H3OH, HCOOCH3, and CH3OCH3, respectively. Interestingly, C2H3OH has an abundance similar to that of its well known isomer acetaldehyde (CH3CHO), with C2H3OH/CH3CHO ~ 1 at the cyanopolyyne peak. We discuss potential formation routes to these molecules and recognize that further experimental, theoretical, and astronomical studies are needed to elucidate the true mechanism of formation of these O-bearing complex organic molecules in cold interstellar sources.

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TMC-1, the starless core sulfur factory: Discovery of NCS, HCCS, H2CCS, H2CCCS, and C4S and detection of C5S

We report the detection of the sulfur-bearing species NCS, HCCS, H2CCS, H2CCCS, and C4S for the first time in space. These molecules were found towards TMC-1 through the observation of several lines for each species. We also report the detection of C5S for the first time in a cold cloud through the observation of five lines in the 31-50 GHz range. The derived column densities are N(NCS) = (7.8 +/- 0.6)e11 cm-2, N(HCCS) = (6.8 +/- 0.6)e11 cm-2, N(H2CCS) = (7.8 +/- 0.8)e11 cm-2, N(H2CCCS) = (3.7 +/- 0.4)e11 cm-2, N(C4S) = (3.8 +/- 0.4)e10 cm-2, and N(C5S) = (5.0 +/- 1.0)e10 cm-2. The observed abundance ratio between C3S and C4S is 340, that is to say a factor of approximately one hundred larger than the corresponding value for CCS and C3S. The observational results are compared with a state-of-the-art chemical model, which is only partially successful in reproducing the observed abundances. These detections underline the need to improve chemical networks dealing with S-bearing species.

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Discovery of the propargyl radical (CH2CCH) in TMC-1: one of the most abundant radicals ever found and a key species for cyclization to benzene in cold dark clouds

We present the first identification in interstellar space of the propargyl radical (CH2CCH). This species was observed in the cold dark cloud TMC-1 using the Yebes 40m telescope. The six strongest hyperfine components of the 2,0,2-1,0,1 rotational transition, lying at 37.46~GHz, were detected with signal-to-noise ratios in the range 4.6-12.3 sigma. We derive a column density of 8.7e13 cm-2 for CH2CCH, which translates to a fractional abundance relative to H2 of 8.7e-9. This radical has a similar abundance to methyl acetylene, with an abundance ratio CH2CCH/CH3CCH close to one. The propargyl radical is thus one of the most abundant radicals detected in TMC-1, and it is probably the most abundant organic radical with a certain chemical complexity ever found in a cold dark cloud. We constructed a gas-phase chemical model and find calculated abundances that agree with, or fall two orders of magnitude below, the observed value depending on the poorly constrained low-temperature reactivity of CH2CCH with neutral atoms. According to the chemical model, the propargyl radical is essentially formed by the C + C2H4 reaction and by the dissociative recombination of C3Hn+ ions with n = 4-6. The propargyl radical is believed to control the synthesis of the first aromatic ring in combustion processes, and it probably plays a key role in the synthesis of large organic molecules and cyclization processes to benzene in cold dark clouds.

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Discovery of allenyl acetylene, H2CCCHCCH, in TMC-1. A study of the isomers of C5H4

We present the discovery in TMC-1 of allenyl acetylene, H2CCCHCCH, through the observation of nineteen lines with a signal-to-noise ratio ~4-15. For this species, we derived a rotational temperature of 7 +/- 1 K and a column density of (1.2 +/- 0.2)e13 cm-2. The other well known isomer of this molecule, methyl diacetylene (CH3C4H), has also been observed and we derived a similar rotational temperature, Trot = 7.0 +/- 0.3 K, and a column density for its two states (A and E) of (6.5 +/- 0.3)e12 cm-2. Hence, allenyl acetylene and methyl diacetylene have a similar abundance. Remarkably, their abundances are close to that of vinyl acetylene (CH2CHCCH). We also searched for the other isomer of C5H4, HCCCH2CCH (1.4-pentadiyne), but only a 3sigma upper limit of 2.5e12 cm-2 to the column density can be established. These results have been compared to state-of-the-art chemical models for TMC-1, indicating the important role of these hydrocarbons in its chemistry. The rotational parameters of allenyl acetylene have been improved by fitting the existing laboratory data together with the frequencies of the transitions observed in TMC-1.

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