Formation of Complex Organic Molecules (COMs) from Polycyclic Aromatic Hydrocarbons (PAHs): Implications for ISM IR Emission Plateaus and Solar System Organics (original) (raw)

2020, ACS Earth and Space Chemistry

The presence of complex organic molecules (COMs) in a variety of solar system objects has prompted various theories regarding their origins. This paper reports on a series of proton, electron, and UV radiation experiments, conducted singly and in combination, on polycyclic aromatic hydrocarbon (PAH) thin films to determine if PAH-related materials could be related to COMs. Fourier transform infrared (FTIR) and mass spectra reveal that the PAHs are fragmented and altered, producing new infrared features and a mass spectral pattern similar to those from small aliphatic and larger saturated hydrocarbon chain and ring systems. Mass spectra after proton and electron irradiation exhibit significant differences. The proton irradiation products appear to contain more oxygen-related species, possibly the result of higher H 2 O concentrations in the vacuum chamber, whereas electron irradiation generates a more abundant, larger mass organic species mass spectral pattern. Combined irradiation produces a superposition of the proton and electron results, with some subtle differences. Mass spectral patterns resulting from electron and combined irradiation compare favorably to Cassini ion neutral mass spectrometer (INMS) measurements of particles falling from Saturn's inner rings into its upper atmosphere. FTIR results are compared to PAH emission from interstellar sources and absorption components in IR spectra observed toward low-mass young stellar objects (YSOs). Notably, some newly reported broad IR features appear very similar in structure to the plateaus underlying the astronomical 3.2−3.6, 6−9, and 10−15 μm emission plateaus and several of the absorption components found in spectra observed toward YSOs. The studies also indicate that the presence of other species, such as H 2 O, may significantly impact the radiation products. These results point to the fact that a top-down synthesis of solar system COMs is possible via irradiative processing of PAHs.

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Complex organic matter in space: about the chemical composition of carriers of the Unidentified Infrared Bands (UIBs) and protoplanetary emission spectra recorded from certain astrophysical objects

Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life, 2004

In this communication we present the basic concept that the pure PAHs (Polycyclic Aromatic Hydrocarbons) can be considered only the ideal carriers of the UIBs (Unidentified Infrared Bands), the emission spectra coming from a large variety of astronomical objects. Instead we have proposed that the carriers of UIBs and of protoplanetary nebulae (PPNe) emission spectra are much more complex molecular mixtures possessing also complex chemical structures comparable to certain petroleum fractions obtained from the petroleum refining processes. The demonstration of our proposal is based on the comparison between the emission spectra recorded from the protoplanetary nebulae (PPNe) IRAS 22272+ 5435 and the infrared absorption spectra of certain 'heavy' petroleum fractions. It is shown that the best match with the reference spectrum is achieved by highly aromatic petroleum fractions. It is shown that the selected petroleum fractions used in the present study are able to match the band...

Spectroscopy of large PAHs. Laboratory studies and comparison to the Diffuse Interstellar Bands

Astronomy & Astrophysics, 2002

Polycyclic Aromatic Hydrocarbons (PAHs) are thought to be the carriers of the ubiquitous infrared emission bands (UIBs). Data from the Infrared Space Observatory (ISO) have provided new insights into the size distribution and the structure of interstellar PAH molecules pointing to a trend towards larger-size PAHs. The mid-infrared spectra of galactic and extragalactic sources have also indicated the presence of 5-ring structures and PAH structures with attached side groups. This paper reports for the first time the laboratory measurement of the UV-Vis-NIR absorption spectra of a representative set of large PAHs that have also been selected for a long duration exposure experiment on the International Space Station ISS. PAHs with sizes up to 600 amu, including 5-ring species and PAHs containing heteroatoms, have been synthesized and their spectra measured using matrix isolation spectroscopy. The spectra of the neutral species and the associated cations and anions measured in this work are also compared to astronomical spectra of Diffuse Interstellar Bands (DIBs).

PAHs in Astronomy - A Review

Proceedings of The International Astronomical Union, 2008

Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of organic matter in space. Their contribution is invoked in a broad spectrum of astronomical observations that range from the ultraviolet to the far-infrared and cover a wide variety of objects and environments from meteorites and interplanetary dust particles to outer Solar System bodies to the interstellar medium in the local Milky Way and in other galaxies. Extensive efforts have been devoted in the past two decades to experimental, theoretical, and observational studies of PAHs. A brief review is given here of the evidence obtained so far for the contribution of PAHs to the phenomena aforementioned. An attempt is made to distinguish the cases where solid evidence is available from cases where reasonable assumptions can be made to the cases where the presence -or the absence -of PAHs is purely speculative at this point.

Mid‐Infrared Spectra of Polycyclic Aromatic Hydrocarbon Emission in Herbig Ae/Be Stars

The Astrophysical Journal, 2005

We present spectra of four Herbig AeBe stars obtained with the Infrared Spectrograph (IRS) 1 on the Spitzer Space Telescope. All four of the sources show strong emission from polycyclic aromatic hydrocarbons (PAHs), with the 6.2 µm emission feature shifted to 6.3 µm and the strongest C−C skeletal-mode feature occuring at 7.9 µm instead of at 7.7 µm as is often seen. Remarkably, none of the four stars have silicate emission. The strength of the 7.9 µm feature varies with respect to the 11.3 µm feature among the sources, indicating that we have observed PAHs with a range of ionization fractions. The ionization fraction is higher for systems with hotter and brighter central stars. Two sources, HD 34282 and HD 169142, show emission features from aliphatic hydrocarbons at 6.85 and 7.25 µm. The spectrum of HD 141569 shows a previously undetected emission feature at 12.4 µm which may be related to the 12.7 µm PAH feature. The spectrum of HD 135344, the coolest star in our sample, shows an unusual profile in the 7-9 µm region, with the peak emission to the red of 8.0 µm and no 8.6 µm PAH feature.

On the Viability of the Pah Model as an Explanation of the Unidentified Infrared Emission Features

The Astrophysical Journal, 2014

Polycyclic aromatic hydrocarbon (PAH) molecules are widely considered the preferred candidate for the carrier of the unidentified infrared emission bands observed in the interstellar medium and circumstellar envelopes. In this paper, we report the results of fitting a variety of non-PAH spectra (silicates, hydrogenated amorphous carbon, coal, and even artificial spectra) using the theoretical infrared spectra of PAHs from the NASA Ames PAH IR Spectroscopic Database. We show that these non-PAH spectra can be well fitted by PAH mixtures. This suggests that a general match between astronomical spectra and those of PAH mixtures does not necessarily provide definitive support for the PAH hypothesis.

Spectroscopy of PAH molecules and ions: From the laboratory to astronomical observations

2007

An extensive program has been developed to characterize the physical and chemical properties of carbon molecules and ions in space and to describe how they influence the radiation and energy balance. We review recent progress in the experimental and observational studies of an important class of carbon materials (PAHs) in the diffuse interstellar medium and discuss global astrophysical implications and future directions.

Spectroscopy of large PAHs

Astronomy and Astrophysics, 2002

Polycyclic Aromatic Hydrocarbons (PAHs) are thought to be the carriers of the ubiquitous infrared emission bands (UIBs). Data from the Infrared Space Observatory (ISO) have provided new insights into the size distribution and the structure of interstellar PAH molecules pointing to a trend towards larger-size PAHs. The mid-infrared spectra of galactic and extragalactic sources have also indicated the presence of 5-ring structures and PAH structures with attached side groups. This paper reports for the first time the laboratory measurement of the UV-Vis-NIR absorption spectra of a representative set of large PAHs that have also been selected for a long duration exposure experiment on the International Space Station ISS. PAHs with sizes up to 600 amu, including 5-ring species and PAHs containing heteroatoms, have been synthesized and their spectra measured using matrix isolation spectroscopy. The spectra of the neutral species and the associated cations and anions measured in this work are also compared to astronomical spectra of Diffuse Interstellar Bands (DIBs).

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