Molecular spectroscopy in astrophysics: the case of polycyclic aromatic hydrocarbons (original) (raw)
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Interstellar Chemistry: A Strategy for Detecting Polycyclic Aromatic Hydrocarbons in Space
Journal of the American Chemical Society, 2005
Polycyclic aromatic hydrocarbons (PAHs) have long been postulated as constituents of the interstellar gas and circumstellar disks. Observational infrared emission spectra have been plausibly interpreted in support of this hypothesis, but the small (or zero) dipole moments of planar, unsubstituted PAHs preclude their definitive radio astronomical identification. Polar PAHs, such as corannulene, thus represent important targets for radio astronomy because they offer the possibilities of confirming the existence of PAHs in space and revealing new insight into the chemistry of the interstellar medium. Toward this objective, the high-resolution rotational spectrum of corannulene has been obtained by Fourier transform microwave spectroscopy, and the dipole moment (2.07 D) of this exceptionally polar PAH has been measured by exploiting the Stark effect.
The Astrophysical Journal Supplement Series, 2013
Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (CH 3), methylene (CH 2), or diamond-like CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR) spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF). Supported by calculations at the density functional theory (DFT) level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium (ISM) at 3.4 µm and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CH x groups (x = 1,2,3) would contribute approximately in equal quantities to the 3.4 µm feature (N CHx / N H ≈ 10 −5 − 2 × 10 −5). The abundances, however, may be two to four times lower if a major contribution to the 3.4 µm feature comes from molecules in the gas phase. Aromatic CH groups seem to be almost absent from some lines of sight, but can be nearly as abundant as each of the aliphatic components in other directions (N CH / N H 2 × 10 −5 ; upper value for grains). Due to comparatively low binding energies, astronomical IR emission sources do not display such heavy excess hydrogenation. At best, especially in proto-planetary nebulae, CH 2 groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star.
The Astrophysical Journal, 2017
The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 µm ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs may have an aliphatic component as revealed by the detection in many UIE sources of the aliphatic C-H stretching feature at 3.4 µm. The ratio of the observed intensity of the 3.4 µm feature to that of the 3.3 µm aromatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers. This requires the knowledge of the intrinsic oscillator strengths of the 3.3 µm aromatic C-H stretch (A 3.3) and the 3.4 µm aliphatic C-H stretch (A 3.4). Lacking experimental data on A 3.3 and A 3.4 for the UIE candidate materials, one often has to rely on quantum-chemical computations. Although the second-order Møller-Plesset (MP2) perturbation theory with a large basis set is more accurate than the B3LYP density functional theory, MP2 is computationally very demanding and impractical for large molecules. Based on methylated PAHs, we show here that, by scaling the band strengths computed at an inexpensive level (e.g., B3LYP/6-31G *) we are able to obtain band strengths as accurate as that computed at far more expensive levels (e.g., MP2/6-311+G(3df,3pd)). We calculate the model spectra of methylated PAHs and their cations excited by starlight of different spectral shapes and intensities. We find (I 3.4 /I 3.3) mod , the ratio of the model intensity of the 3.4 µm feature to that of the 3.3 µm feature, is insensitive to the spectral shape and intensity of the exciting starlight. We derive a straightforward
Based on theoretical spectra computed using Density Functional Theory we study the properties of polycyclic aromatic hydrocarbons (PAH). In particular using bin-average spectra of PAH molecules with varying number of carbons we investigate how the intensity of the mid-infrared emission bands, 3.3, 6.2, 7.7, and 11.3 μm, respond to changes in the number of carbons, charge of the molecule, and the hardness of the radiation field that impinges the molecule. We confirm that the 6.2/7.7 band ratio is a good predictor for the size of the PAH molecule (based on the number of carbons present). We also investigate the efficacy of the 11.3/3.3 ratio to trace the size of PAH molecules and note the dependence of this ratio on the hardness of the radiation field. While the ratio can potentially also be used to trace PAH molecular size, a better understanding of the impact of the underlying radiation field on the 3.3 μm feature and the effect of the extinction on the ratio should be evaluated. The newly developed diagnostics are compared to band ratios measured in a variety of galaxies observed with the Infrared Spectrograph on board the Spitzer Space Telescope. We demonstrate that the band ratios can be used to probe the conditions of the interstellar medium in galaxies and differentiate between environments encountered in normal star forming galaxies and active galactic nuclei. Our work highlights the immense potential that PAH observations with the James Webb Space Telescope will have on our understanding of the PAH emission itself and of the physical conditions in galaxies near and far.
A Multiscale Study of Polycyclic Aromatic Hydrocarbon Properties in Galaxies
2008
In the present contribution, I summarize a systematic study of ISO and Spitzer mid-IR spectra of Galactic regions and star forming galaxies. This study quantifies the relative variations of the main aromatic features inside spatially resolved objects as well as among the integrated spectra of 50 objects. Our analysis implies that the properties of the PAHs are remarkably universal throughout our sample and at different spatial scales. In addition, the relative variations of the band ratios, as large as one order of magnitude, are mainly controled by the fraction of ionized PAHs. In particular, I show that we can rule out both the modification of the PAH size distribution and the mid-IR extinction, as an explanation of these variations. High values of the I(6.2)/I(11.3) ratio are found to be associated with the far-UV illuminated surface of PDRs, at the scale of an interstellar cloud, and associated with star formation activity, at the scale of a galaxy. Using a few well-studied Gala...
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).
Polycyclic Aromatic Hydrocarbons and the Diffuse Interstellar Bands: A Survey
Astrophysical Journal, 1999
We discuss the proposal relating the origin of some of the di †use interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons (PAHs) present in interstellar clouds. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices, are compared with the spectra of Ðve reddened early-type stars selected from an extensive set of astronomical spectra. From this comparison, it is concluded that PAH ions are good candidates to explain some of the DIBs. Unambiguous assignments are difficult, however, because of the shift in wavelengths and the band broadening induced in the laboratory spectra by the solid matrix. This situation is illustrated by a comparison with the gas-phase spectra made available recently for two PAH ions. DeÐnitive band assignments and, ultimately, the test of the proposal that PAH ions carry some of the DIBs must await the availability of a larger set of gas-phase measurements in the laboratory. The present assessment o †ers a guideline for future laboratory experiments by allowing the preselection of promising PAH molecules to be studied in jet expansions.