Large polycyclic aromatic hydrocarbon (PAH) molecules carry the infrared (IR) emission features that dominate the spectra of most galactic and extragalactic sources. This review surveys the observed mid-IR characteristics of these emission features and summarizes laboratory and theoretical studies of the spectral characteristics of PAHs and the derived intrinsic properties of emitting interstellar PAHs. Dedicated experimental studies have provided critical input for detailed astronomical models that probe the origin and evolution of interstellar PAHs and their role in the universe. The physics and chemistry of PAHs are discussed, emphasizing the contribution of these species to the photoelectric heating and the ionization balance of the interstellar gas and to the formation of small hydrocarbon radicals and carbon chains. Together, these studies demonstrate that PAHs are abundant, ubiquitous, and a dominant force in the interstellar medium of galaxies.

Interstellar Polycyclic Aromatic Hydrocarbon Molecules

We present a quantitative model for the infrared emission from dust in the diffuse interstellar medium. The model consists of a mixture of amorphous silicate grains and carbonaceous grains, each with a wide size distribution ranging from molecules containing tens of atoms to large grains 1 μm in diameter. We assume that the carbonaceous grains have properties like polycyclic aromatic hydrocarbons (PAHs) at very small sizes and graphitic properties for radii a 50 A. On the basis of recent laboratory studies and guided by astronomical observations, we propose astronomical absorption cross sections for use in modeling neutral and ionized PAHs from the far-ultraviolet to the far-infrared. We also propose modifications to the far-infrared emissivity of astronomical silicate. We calculate energy distribution functions for small grains undergoing temperature spikes caused by stochastic absorption of starlight photons using realistic heat capacities and optical properties. Using a grain-size distribution consistent with the observed interstellar extinction, we are able to reproduce the near-IR to submillimeter emission spectrum of the diffuse interstellar medium, including the PAH emission features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm. The model is compared with the observed emission at high Galactic latitudes as well as in the Galactic plane, as measured by the COBE/DIRBE, COBE/FIRAS, IRTS/MIRS, and IRTS/NIRS instruments. The model has 60 × 10-6 of C (relative to H) locked up in PAHs, with 45 × 10-6 of C in a component peaking at ~6 A (NC ≈ 100 carbon atoms) to account for the PAH emission features and with 15 × 10-6 of C in a component peaking at ~50 A to account for the 60 μm flux. The total infrared emission is in excellent agreement with COBE/DIRBE observations at high Galactic latitudes, just as the albedo for our grain model is in accord with observations of the diffuse Galactic light. The aromatic absorption features at 3.3 and 6.2 μm predicted by our dust model are consistent with observations. We calculate infrared emission spectra for our dust model heated by a range of starlight intensities, from 0.3 to 104 times the local interstellar radiation field, and we tabulate the intensities integrated over the SIRTF/IRAC and MIPS bands. We also provide dust opacities tabulated from the extreme-ultraviolet to submillimeter wavelengths.

https://iopscience.iop.org/article/10.1086/323147/pdf

Infrared Emission from Interstellar Dust. II. The Diffuse Interstellar Medium

▪ Abstract Our understanding of the evolution of organic molecules, and their voyage from molecular clouds to the early solar system and Earth, has changed dramatically. Incorporating recent observ...

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Organic Molecules in the Interstellar Medium, Comets, and Meteorites: A Voyage from Dark Clouds to the Early Earth

Stellar nucleosynthesis of heavy elements, followed by their subsequent release into the interstellar medium, enables the formation of stable carbon compounds in both gas and solid phases. Spectroscopic astronomical observations provide evidence that the same chemical pathways are widespread both in the Milky Way and in external galaxies. The physical and chemical conditions—including density, temperature, ultraviolet radiation and energetic particle flux—determine reaction pathways and the complexity of organic molecules in different space environments. Most of the organic carbon in space is in the form of poorly-defined macromolecular networks. Furthermore, it is also unknown how interstellar material evolves during the collapse of molecular clouds to form stars and planets. Meteorites provide important constraints for the formation of our Solar System and the origin of life. Organic carbon, though only a trace element in these extraterrestrial rock fragments, can be investigated in great detail with sensitive laboratory methods. Such studies have revealed that many molecules which are essential in terrestrial biochemistry are present in meteorites. To understand if those compounds necessarily had any implications for the origin of life on Earth is the objective of several current and future space missions. However, to address questions such as how simple organic molecules assembled into complex structures like membranes and cells, requires interdisciplinary collaborations involving various scientific disciplines. Introduction Life in the Universe is the consequence of the increasing complexity of chemical pathways which led to stable carbon compounds assembling into cells and higher organisms.

/pdf/a-voyage-from-dark-clouds-to-the-early-earth-hw01qkx5z0.pdf

A voyage from dark clouds to the early Earth

Molecular absorption and emission bands dominate the visible, infrared, and submillimeter spectra of most objects with associated gas. These observations reveal a surprisingly rich array of molecular species and attest to a complex chemistry taking place in the harsh environment of the interstellar medium of galaxies. Molecules are truly everywhere and an important component of interstellar gas. This review surveys molecular observations in the various spectral windows and summarizes the chemical and physical processes involved in the formation and evolution of interstellar molecules. The rich organic inventory of space reflects the multitude of chemical processes involved that, on the one hand, build up molecules an atom at a time and, on the other hand, break down large molecules injected by stars to smaller fragments. Both this bottom-up and the trickle-down chemistry are reviewed. The emphasis is on understanding the characteristics of complex polycyclic aromatic hydrocarbon molecules and fullerenes and their role in chemistry as well as the intricate interaction of gas-phase ion-molecule and neutral-neutral reactions and the chemistry taking place on grain surfaces in dense clouds in setting the organic inventory of regions of star and planet formation and their implications for the chemical history of the Solar System. Many aspects of molecular astrophysics are illustrated with recent observations of the HIFI instrument on the Herschel Space Observatory.

https://cab.inta-csic.es/molecular_universe_2011/pressroomNew/tielensInterview.pdf

The molecular universe

Size effects on dissociation rates of polycyclic aromatic hydrocarbon cations : laboratory studies and astrophysical implications

Following a previous experimental study of the photostability of a series of polycyclic aromatic hydrocarbons (PAHs) this work extends to irregularly shaped PAHs, methyl-substituted PAHs, and related compounds. A photostability index R has been devised, which measures the propensity for H-loss of PAH monocations relative to that for regular catacondensed or pericondensed PAHs containing the same number of atoms. This index is also valid, to a good approximation, for neutral PAHs. Structural effects (presence of a methyl group; dihydro groups; H-H steric hindrance; degree of π conjugation; isomers) and size-dependent effects on R are demonstrated and discussed. Astrophysical applications of the propensity of PAH photodissociation include an estimation of the maximum amount of energy that can be deposited in the nascent parent PAH ion in H I regions, and an evaluation of the lower limit to the size of photostable PAHs in these regions, for various types of PAHs and their derivatives. The results provide a possible explanation for the existence of a limited number of PAHs in the ISM as required by the interstellar carbon budget determined by Snow & Witt. The information obtained is also relevant to interpretation of the presence and formation of PAHs and their methyl derivatives in meteoritic, micrometeoritic, cometary, and interplanetary particle materials.

https://iopscience.iop.org/article/10.1086/306752/pdf

H. Baumgärtel

Papers

Size effects on dissociation rates of polycyclic aromatic hydrocarbon cations : laboratory studies and astrophysical implications

Structure-dependent Photostability of Polycyclic Aromatic Hydrocarbon Cations: Laboratory Studies and Astrophysical Implications