Nanocosmos confirms there are PAHs in the interstellar medium

Image of the Heiles Cloud 2 as part of the massive Taurus Molecular Cloud (TMC). The magnifying glass shows the region, called TMC-1, where our line survey observations were made. Image captured at Grand Mesa Observatory in Colorado (USA). Image credit and copyright Terry Hancock and Tom Masterson.

First detection of a pure PAH (indene c-C9H8) in an unexpected place!

Polycyclic Aromatic Hydrocarbons (PAHs) are organic compounds formed by rings. Their bad reputation on Earth is due to their toxicity, as they are mostly the result of oil and coal combustion. However, in space they have another role that, despite waiting for confirmation, may be related even to the origin of life.

In the interstellar medium observations, there are infrared bands that, until now, were unidentified. The hypothesis (for more than 40 years) was that these bands were probably PAHs, but final confirmation was lacking.

The first milestone of this work is the confirmation, for the first time, of the presence of a pure PAH (indene) in the interstellar medium. The second milestone is that we have confirmed the discovery in an unexpected place: a cold dark cloud called TMC-I.

The TMC-1 cold dark cloud

It was originally thought that PAHs could form in circumstellar envelopes around evolved stars. These stars are in the final stages of their lives and expel much of their matter into the interstellar medium. In fact, twenty years ago benzene, (an aromatic ring present in many PAHs) was first detected in the hot and ultraviolet light illuminated regions around an evolved star. This made astronomers think that the formation of PAHs requires high temperatures and ultraviolet radiation. Therefore, the presence of PAHs in the interstellar medium would have an exogenous origin. That is, PAHs would form in circumstellar envelopes and would later be dragged into the interstellar medium by stellar winds.

However, the first detection has been carried out in an unexpected environment: the cold pre-stellar core TMC-1 in the Taurus Molecular Cloud complex, which is well protected from ultraviolet radiation. In this environment, in addition to the indene (c-C9H8), the presence of ethynyl cyclopropenylidene (c-C3HCCH) and cyclopentadiene (c-C5H6) has been detected. It should be noted that cyclopentadiene and indene, molecules formed by rings of five and six carbon atoms, are exceptionally abundant despite their large size.

With these observations, it is demonstrated not only the unambiguous presence of PAHs in the interstellar medium, but also that they are formed in situ and from less complex molecules. They are not dragged from other environments (e.g. on the surface of dust grains), but are formed according to what is called a bottom-up formation mechanism, that is, from smaller molecules that join in the gas phase.

Although some theories relate PAHs to the origin of life, more studies are still needed to confirm the role they could have played in the formation of nucleobases, which are part of the RNA. While astronomers gather more data that may or may not confirm this hypothesis, this NANOCOSMOS-ERC discovery is a major breakthrough in our current understanding to explain the formation mechanisms of complex molecules, which remain, for the most part, a mystery.

The Yebes 40m radio telescope

The TMC-1 observations have been carried out with the 40m radio telescope at Yebes Observatory (IGN, the Spanish National Geographic Institute). This was possible thanks to the Nanocosmos new receivers, built within the Nanocosmos-ERC project, funded by the European Research Council. Since they were installed, these high-sensitivity new receivers are providing valuable new information on the interstellar medium.

More information

Pure hydrocarbon cycles in TMC-1: Discovery of ethynyl cyclopropenylidene, cyclopentadiene and indene (Astronomy & Astrophysics, May 2021, DOI: 10.1051/0004-6361/202141156). Authors: J. Cernicharo, M. Agúndez, C. Cabezas, B. Tercero, N. Marcelino, J. R. Pardo, & P. de Vicente.

AstroPAH: A Newsletter on Astronomical PAHs (Leiden University, the Netherlands), issue 78, May 21, 2021. A new golden age era for Astrochemistry: Discovering PAHs with millikelvin sensitive radio astronomical molecular line surveys (by Prof. José Cernicharo, on behalf of the NANOCOSMOS ERC team).

CSIC press release: Hallados hidrocarburos policíclicos aromáticos en el medio interestelar

IGN press release: Hidrocarburos policíclicos aromáticos en el medio interestelar

El Mundo newspaper (May 22, 2021): ¿Por qué es importante el indeno hallado en el espacio por astrónomos españoles? (by Dr. Rafael Bachiller, director of the Observatorio Astronómico Nacional, IGN, Madrid).

Breaking: First Time Discovery of the PAH Indene in Space

The NANOCOSMOS team reports the first time detection of the simplest polycyclic aromatic hydrocarbon (PAH) carrying a five-membered ring—indene (c-C9H8) in Space (TMC-1 cold dark molecular cloud) with rotational spectroscopy. This major challenging breakthrough is the first step to understand the potential formation mechanisms of these species in the interstellar medium. Moreover, the team derives a high abundance of indene that needs to be explained through alternative and efficient chemical routes.

The team also reports the first time discovery in space of two other organic compounds, the c-C3HCCH (ethynyl cyclopropenylidene), and c-C5H6 (cyclopentadiene).

These discoveries are the result from the groundbreaking Yebes 40m Observatory sensitive survey with the new NANOCOSMOS Q-band receiver of the TMC-1 cold molecular cloud. This survey has led to the discovery of multiple molecular species since 2020 with more than 25 molecules, 15 of them for the first time in Space.

The best for NANOCOSMOS is yet to come. Stay tuned!

Pure hydrocarbon cycles in TMC-1: Discovery of ethynyl cyclopropenylidene, cyclopentadiene and indene (Accepted for publication in A&A Letters, 2021). Authors: J. Cernicharo, M. Agúndez, C. Cabezas, B. Tercero, N. Marcelino, J. R. Pardo, & P. de Vicente.

High-resolution Infrared Observations

Discovery of molecular species in IRC+10216Diacetylene (C4H2)Major emission arises at 50 AU or less from the star in the dust formation zone. Constraints on chemical models
Distribution of molecular emission in IRC+10216Ethylene (C2H4)Part of the emission arises in the inner dust formation zone contrary to previous findings. Constraints on chemical models
Detection of molecular emission in R LeoCO2 Infrared fluorescence More systematic study of the CO2 emission in O-rich stars to understand how CO2 forms
Major NANOCOSMOS highlights in “High spectral resolution IR observations” (see dedicated descriptions below)

High spectral resolution infrared observations of circumstellar envelopes – CSEs – in AGB stars are essential to study important molecular species with no permanent dipole moment (e.g. H2, O2, CO2, SiH4, C2H4). This lack makes them undetectable in the millimeter range due to the absence of rotational transitions. Hence, the best possible observation of these molecules is through its vibration–rotation lines in the mid infrared range.

These observations are vital to study the amount of ejected matter in the pulsation phase and determine the chemical interactions between the ejected molecules in the CSEs. These studies help improve the underlying assumptions of currently available chemical models.

Therefore, we observed the carbon-rich star IRC+10216 with the Texas Echelon-cross-Echelle Spectrograph (TEXES) on the 3 m Infrared Telescope Facility (IRTF). We carried out observations of the oxygen rich star R Leo with the Stratospheric Observatory for Infrared Astronomy (SOFIA) with the high spectral resolution Echelon-cross-Echelle Spectrograph (EXES). Finally, we used both SOFIA/EXES and IRTF/TEXES to observe the carbon rich semi-regular star Y CVn.

Our IR observations have led to the discovery of diacetylene (C4H2) in the envelope of IRC+10216 with the major emission arising in the dust formation zone at less than 50 AU from the center of the star. Ethylene (C2H4) shows emission from the inner dust formation zone in IRC+10216 contrary to previous findings. These studies pose further constraints on current chemical models.

Summary of oustanding results with the NANOCOSMOS high-resolution infrared observations of CSEs in AGB stars

Multi-frequency high spectral resolution observations of HCN toward the circumstellar envelope of Y CVn (J. P. Fonfría et al., A&A, 07/2021)

  • Analysis and Identification of 130 lines of HCN and H13CN with either P-Cygni profiles or pure absorption profiles
  • Dust grains could be mostly made of silicon carbide SiC in the inner layers of the CSE (~ 3.5 stellar radii) and of amorphous carbon in the outer envelope (up to 200 stellar radii)
  • The observed mid-IR lines are broader than expected due to possible high velocity matter ejections or photospheric movements related to stellar pulsation or convection.
  • HCN rotational and vibrational temperatures are out of local thermodynamics equilibrium so collisions do not play any role in the gas thermalization

Detection of infrared fluorescence of carbon dioxide in R Leonis with SOFIA/EXES (J. P. Fonfría et al., A&A, 11/2020)

  • CO2 (≃240 emission lines in the range 12.8−14.3 μm) New detection in R Leo
  • The observed CO2 lines can be grouped into three different populations, (warm, hot, and very hot), with approximate temperatures of 550, 1150, and 1600 K
  • The CO2 emitting regions at 1600, 1150, and 550 K are located at 2.2, 3.5, and 10 stellar radii from the center of R Leo
  • We need a systematic study of the CO2 emission in O-rich stars to understand how this molecule forms and the possible dependence of the column density on the mass-loss rate

Carbon Chemistry in IRC+10216: Infrared Detection of Diacetylene (J. P. Fonfría et al., ApJ, 01/2018)

  • C4H2 (24 absorption features in the range 8.0 to 8.1 μm) First detection in IRC+10216
  • The major emission of C4H2 arises in the dust formation zone at radii lower than 20 stellar radii (50 Astronomical Units) from the center of IRC+10216
  • Our photochemical models underestimate the observed C4H2 abundance. This finding could imply that the molecules in the envelope are photodissociated in shells closer to the star than is commonly assumed
  • More info on diacetylene: Astromolecule of the Month

The Abundance of C2H4 in the Circumstellar Envelope of IRC+10216 (J. P. Fonfría et al., ApJ, 01/2017)

  • C2H4 (80 ro-vibrational features in absorption) Part of the emission arises in the inner dust formation zone contrary to previous findings
  • Part of the emission of ethylene arises in the dust formation zone at radii between 14 and 28 stellar radii from the center of IRC+10216, with no evidence of C2H4 closer to the star. Previous findings supposed all C2H4 arises in the far outer envelopes.
  • Our photochemical models underestimate the observed C2H4 terminal abundance by a factor of 4. We estimate that a fraction of the ethylene gas-phase could condense onto the dust grains around 20 stellar radii. this fact could affect the chemistry evolution of the envelope

Yebes 40m broad band receivers

IRC+10216: Discovery of molecular speciesHC9N (first time in Space), HC7N, MgC3N and MgC4HFormation in the external layers of the circumstellar envelope
TMC-1: Discovery of molecular species25 molecules, including 1 PAH (indene), 2 hydrocarbon cycles, 3 protonated forms and 2 nitrile anions (15 of them, first time in Space)See dedicated descriptions below
Complementary laboratory experimentsHDCCN, CH3CO+, HC3S+ and HC3O+Laboratory production and full spectroscopical characterization
Table: Major NANOCOSMOS highlights with the “Yebes 40m broad band receivers” (see dedicated descriptions below)

NANOCOSMOS successfully designed and constructed two new millimeter broad band receivers for the Q frequency band (31.5 − 50 GHz) and the W band (72 − 90.5 GHz) for the Yebes 40m radio telescope. One of our main achievements is the instantaneous frequency coverage in order to observe many molecular transitions with single tunings in single-dish mode.

Our Yebes observations have led to the discovery of multiple molecular species. These were made in 2019 (Q2, Q4), and 2020 (Q1) and were complemented with the IRAM 30m radio telescope in Granada (W band).

  • Objects: IRC+10216 as the archetypal AGB carbon rich star and the cold dark Taurus Molecular Cloud -1 or TMC-1.
  • Methodology: observations, laboratory characterization, ab-initio quantum calculations, rotational diagrams, gas-phase chemical models and radiative transfer calculations.

Summary of results with the NANOCOSMOS mm broad band receivers at Yebes 40m radio telescope:

Detection of vibrationally excited HC7N and HC9N in IRC+10216 (J. R. Pardo et al., A&A, 08/2020)

  • HC9N (26 doublets, vib. exc.) – First time detection and characterization in Space
  • HC7N (17 doublets, vib. exc.) – New detection
  • Emission arising from the external layers of the circumstellar envelope
  • Possibe effects on intensity line variations with the stellar phase
  • These vibrationally excited states must be taken into account for precise abundance determinations of long carbon chains

MgCCCN (top) and MgCCCCH (bottom) optimized structures

Discovery of two new magnesium-bearing species in IRC+10216: MgC3N and MgC4H (J. Cernicharo et al., A&A, 10/2019)

  • MgC3N (16 doublets) – New detection
  • MgC4H (6 doublets) – New detection
  • MgCCH (2 doublets) – Confirmation

TMC-1, the starless core sulfur factory: Discovery of NCS, HCCS, H2CCS, H2CCCS, and C4S and detection of C5S (J. Cernicharo et al., A&A, 04/2021)

  • Sulfur-bearing species NCS, HCCS, H2CCS, H2CCCS, and C4S – First time discovery in Space (TMC-1)
  • C5S – First time detection in a cold dark cloud (TMC-1)
  • State-of-the-art gas-phase chemical networks fail to reproduce the observed column densities. Thus, important reactions involving S and S+(neutral-neutral, neutral-ion) and those on dust grain surfaces are missing and much laboratory and theoretical work need be performed in order to understand the chemistry of sulfur
  • The analysis of C4S and C5S shows that S-bearing carbon chains do not follow the smooth decrease in abundance observed in cold dark molecular clouds and circumstellar envelopes for other carbon chains such as cyanopolyynes (HC2n + 1N; a factor 3–5 between members of this molecular species)

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 (M. Agúndez et al., A&A, 03/2021)

  • Propargyl radical (CH2CCH) 6 strongest hyperfine components of the 20, 2–10, 1 rotational transition – First time discovery in interstellarr Space (TMC-1)
  • Similar abundance as methyl acetylene. Thus, it is one of the most abundant radicals detected in TMC-1. Moreover, it is probably the most abundant organic radical with a certain chemical complexity ever found in a cold dark cloud
  • The observed high abundance, points out that CH2CCH probably plays a key role in the synthesis of large organic molecules and, in particular, the cyclization towards the first aromatic ring (benzene). This also happens in combustion processes where the CH2CCH radical has a key role in the synthesis of benzene and polycyclic aromatic hydrocarbons (PAHs).

Discovery of allenyl acetylene, H2CCCHCCH, in TMC-1. A study of the isomers of C5H4 (J. Cernicharo et al., A&A, 03/2021)

  • Allenyl Acetylene (H2CCCHCCH) 19 rotational transitions – First time detection in Space (TMC-1)
  • We find that allenyl acetylene and methyl diacetylene are the two most stable C5H4 isomers and both have similar observed abundances in TMC-1
  • State-of-the-art chemical models understimate the observed abundances by an order of magnitude. We need to assess the main formation routes in the chemical models, mainly the reactions of the CCH radical with methyl acetylene (CH3CCH) and allene (H2CCCH2)

Discovery of CH2CHCCH and detection of HCCN, HC4N, CH3CH2CN, and, tentatively, CH3CH2CCH in TMC-1 (J. Cernicharo et al., A&A, 03/2021)

  • Vynil Acetylene (CH2CHCCH) – First time detection in Space (TMC-1)
  • HCCN, HC4N, and CH3CH2CN – First time detection in a cold dark cloud (TMC-1)
  • Ethylene could be a likely precursor of CH2CHCCH and CH2CHCN through reactions with CCH and CN, respectively
  • The reaction between CN and vinyl acetylene is a viable route to the C5H3N isomers recently found in TMC-1 at very low temperatures
  • Our observations show that the cyano methylene radical HCCN and the linear cyano ethynyl-methylene radical HC4N have similar abundances unlike predictions from current chemical models

Elegant and fast: the GACELA is running

The Gas Cell chamber

On June 7, 2019, a first paper on the GACELA (GAs CEll for Laboratory Astrophysics) experimental set-up is out at the “Astronomy & Astrophysics” journal (A&A, volume 626, A34, 2019).

More than 3 years have elapsed since the first designs were envisaged for this set-up. Finally, at the end of 2017, the chamber (see figure above) was delivered and successfully tested against leaks. On the other hand, the GACELA broad-band radio receivers (Q and W bands, 31.5–50 and 72–116.5 GHz, respectively) were successfully commissioned in the second semester of 2017 and interfaced with the GACELA set-up in February 2018. Several experimental runs were performed, showing high quality signal-to-noise ratio spectra of molecular species (CH3CN, CH3OH, CH4/N2, CH4/N2/CH3CN, etc).

As stated by the authors, GACELA has achieved an important milestone. It is the first time that we can observe the thermal emission of molecules with an instantaneous band width of 20 GHz in Q band and 3 × 20 GHz in W band for Laboratory Astrophysics. These rotational spectroscopy measurements are complemented by mass spectrometry and optical spectroscopy.

In summary, NANOCOSMOS has developed an elegant and fast-responding set-up, the GACELA, to provide high-resolution and high-sensitivity spectra of molecular species produced in cold plasmas or UV experiments.

More information:

This research was presented in the paper “Broad-band high-resolution rotational spectroscopy for laboratory astrophysics“, published in Astronomy and Astrophysics 626, A34 (29pp), 2019 June 7. The authors are: José Cernicharo (Instituto de Física Fundamental, IFF-CSIC), Juan D. Gallego (Centro de Desarrollos Tecnológicos, Observatorio de Yebes, IGN), José A. López-Pérez (CDT, OY, IGN), Félix Tercero (CDT, OY, IGN), Isabel Tanarro (Instituto de Estructura de la Materia, IEM-CSIC), Francisco Beltrán (CDT, OY, IGN), Pablo de Vicente (CDT, OY, IGN), Koen Lauwaet (Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC & IMDEA Nanociencia), Belén Alemán (ICMM-CSIC & IMDEA Materiales), Elena Moreno (IFF-CSIC), Víctor J. Herrero (IEM-CSIC), José L. Doménech (IEM-CSIC), Sandra I. Ramírez (Centro de Investigaciones Químicas, UAEM, Mexico), Celina Bermúdez (IFF-CSIC), Ramón J. Peláez (IEM-CSIC), María Patino-Esteban (CDT, OY, IGN), Isaac López-Fernández (CDT, OY, IGN), Sonia García-Álvaro (CDT, OY, IGN), Pablo García-Carreño (CDT, OY, IGN), Carlos Cabezas (IFF-CSIC), Inmaculada Malo (CDT, OY, IGN), Ricardo Amils (CDT, OY, IGN), Jesús Sobrado (Centro de Astrobiología, INTA-CSIC), Carmen Díez-González (CDT, OY, IGN), José M. Hernández (IFF-CSIC/CDT, OY, IGN), Belén Tercero (CDT, OY, IGN), Gonzalo Santoro (ICMM-CSIC), Lidia Martínez (ICMM-CSIC), Marcelo Castellanos (IFF-CSIC), Beatriz Vaquero-Jiménez (CDT, OY, IGN), Juan R. Pardo (IFF-CSIC), Laura Barbas (CDT, OY, IGN), José A. López-Fernández (CDT, OY, IGN), Beatriz Aja (Universidad de Cantabria), Arnulf Leuther (Fraunhofer Institut fur Angewandte Festkorperphysik, Germany), José A. Martín-Gago (ICMM-CSIC).

The GACELA experimental set-up is located at the Centro de Desarrollos Tecnológicos, Observatorio de Yebes, thanks to a bilateral agreement between CSIC and IGN for the development of the NANOCOSMOS project.