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).

New theoretical grounds in Astrochemistry

For the first time, NANOCOSMOS has attempted to reproduce the complex molecular chemistry and stardust formation in circumstellar envelopes (CSEs) of asymptotic giant branch (AGB) stars and in cold molecular clouds under accurate and realistic laboratory conditions. These conditions differ from previous studies and techniques to produce stardust analogs, mostly based on laser ablation and pyrolysis, flames, and other far related conditions from those in the CSEs of AGB stars.

These achievements are based on groundbreaking innovative setups at CSIC and CNRS, e.g. Stardust, AROMA, PIRENEA 2 and cold plasma reactors, that foster the study of complex processes that lead to carbon dust formation including polycyclic aromatic hydrocarbons (PAHs) and fullerenes. We have studied the chemistry of atomic silicon and the formation of silicate dust grains. We have also investigated the aromatic content of two different meteorites, Murchison and Almahata Sitta.

In summary, our synergetic results provide significant and surprising breakthroughs in our current understanding of the chemical processes at play in CSEs, the interstellar medium (ISM) and meteoritic samples. These new and open theoretical grounds have also important implications in current chemical models. These NANOCOSMOS breakthroughs are the following:

  • Aliphatic nature of carbonaceous cosmic dust analogs in CSEs. Our realistic laboratory conditions do not lead to the efficient formation of aromatic molecules (PAHs and fullerenes) in the gas phase, contrary to all previous studies (Stardust, AROMA)
  • First detection of a pure PAH (indene) in the TMC-1 cold dark molecular cloud. This is totally an unexpected discovery and suggests an in-situ bottom-up formation process in these environments from smaller molecules in the gas-phase (Yebes 40m radio telescope + new mm receivers).
  • Efficient mechanism for the formation of silane and disilane in the gas phase from Si, H, and H2 in the innermost regions of the CSEs around AGB stars (Stardust).
  • Further evidence for the role of metal (iron) seeds to increase not only the formation of metal clusters but also catalyzed hydrocarbon growth in the CSEs of AGB stars (Cold plasma reactors, AROMA, PIRENEA 2 and ESPOIRS)

First firm detection of fullerenes in meteorites (Almahata Sitta) and co-existence of carbon clusters along with PAHs in this meteorite (AROMA).

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


NANOCOSMOS has successfully achieved significative breakthroughs to address the fundamental problem of cosmic dust formation. We have designed and implemented innovative experimental set-ups and analytical tools well beyond the state-of-the-art. Next we describe the design, construction, implementation and commissioning of these innovations in the dedicated links:

NANOCOSMOS is providing new exciting experimental results in different research fields and challenging theoretical grounds. This menu is devoted to the description and analysis of Outstanding Results and potential new challenges.

Carbon grains around evolved stars

The Nanocosmos team published in October 21, 2019, at Nature Astronomy (available free at Europe PubMed Central), the results of a set of laboratory experiments showing that gas-phase chemistry, under conditions similar to those of a red giant star environment, can produce very efficiently small amorphous carbon grains and carbon chains similar to those found in oil.

Stardust, an ultra-high vacuum machine built in the ERC Nanocosmos project (a Synergy project funded by the European Research Council), was specifically conceived to simulate, with a high level of control, the complex conditions of stardust formation and processing in the environment of evolved stars. In addition, the AROMA setup was built to analyse the molecular content of the samples synthesized by Stardust.

In the words of José Ángel Martín-Gago (Institute of Materials Science of Madrid, ICMM-CSIC, Spain), responsible for the Stardust instrument, “Mimicking the conditions of the envelope of an evolved star, laboratory experiments allow scientists to follow, step by step, the formation process of dust grains, from atoms to simple molecules and their growth to more complex clusters of molecules.”

For José Cernicharo (Institute of Fundamental Physics, IFF-CSIC, Spain), lead co-investigator of the project together with Martín-Gago and Christine Joblin (Institut de Recherche en Astrophysique et Planétologie, IRAP-CNRS, France), “That process is important because those grains of dust, which emerge from the final stages of the evolution of medium-sized stars like our Sun will provide the fundamental pieces needed for the birth of the planets and the main ingredients for the onset of life once injected into the interstellar medium.”

This is why it is essential to develop experiments combining laboratory astrophysics, surface science and astronomical observations to unveil the chemical routes that operate in the inner layers of the envelope of evolved stars.

The results obtained show the formation of amorphous carbon nanograins and aliphatic carbon clusters with traces of aromatic species and no fullerenes. This shows that the latter species cannot form effectively by gas-phase condensation at these temperatures in the zone of the evolved star where the dust is formed, a region that extends up to a few stellar radii.

Chemical complexity

Carbon dust analogues were produced in Stardust and analysed with several characterization techniques including Scanning Tunneling Microscopy and mass spectrometry with the AROMA setup. To produce them only gas carbon atoms and molecular hydrogen were used in a ratio close to that in the atmospheres of AGB stars.

The results showed two types of products: amorphous carbonaceous nanograins – the most abundant, considered to be the main component of carbonaceous star dust – and aliphatic carbon groups. But almost no aromatic molecules were found in the analysis.

According to Joblin, “Polycyclic aromatic hydrocarbons (PAHs) are widespread in massive star-forming regions and in carbon-rich protoplanetary and planetary nebulae. Large carbonaceous molecules like buckminsterfullerene C60 have also been detected in some of these environments. But it seems that they need different conditions to be formed”.

One possible pathway could be through thermal processing of aliphatic material on the surface of dust, which could take place as a result of the significant rise in the temperature of nanograins that occurs in highly UV-irradiated environments. Those results give us new insights into the chemistry of carbonaceous stardust seed formation and foster new observations in order to constrain the physical and chemical conditions in the inner shells of the envelops of evolved stars.

About the ERC

The European Research Council, set up by the European Union in 2007, is the premier European funding organisation for excellent frontier research. Every year it selects and funds the very best, creative researchers of any nationality and age to run projects based in Europe. The ERC has three grant schemes for individual principal investigators – Starting Grants, Consolidator Grants, and Advanced Grants – and Synergy Grants for small groups of excellent researchers.

To date, the ERC has funded more than 9,000 top researchers at various stages of their careers, and over 50,000 postdoctoral fellows, PhD students and other staff working in their research teams. The ERC strives to attract top researchers from anywhere in the world to come to Europe.

The ERC is led by an independent governing body, the Scientific Council. The ERC current President is Professor Jean-Pierre Bourguignon. The ERC has an annual budget of €2 billion for the year 2019. The overall ERC budget from 2014 to 2020 is more than €13 billion, as part of the Horizon 2020 programme, for which European Commissioner for Research, Innovation and Science Carlos Moedas is currently responsible.