Molecular spectroscopy in astrophysics: the case of polycyclic aromatic hydrocarbons (original) (raw)
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
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.
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).
Astrophysical Journal, 2003
We have obtained new Hubble Space Telescope/Space Telescope Imaging Spectrograph spectra to search for structure in the ultraviolet interstellar extinction curve, with particular emphasis on a search for absorption features produced by polycyclic aromatic hydrocarbons (PAHs). The presence of these molecules in the interstellar medium has been postulated to explain the infrared emission features seen in the 3-13 lm spectra of numerous sources. Ultraviolet (UV) spectra are uniquely capable of identifying specific PAH molecules. We obtained high signal-to-noise ratio UV spectra of stars that are significantly more reddened than those observed in previous studies. These data put limits on the role of small (30-50 carbon atoms) PAHs in UV extinction and call for further observations to probe the role of larger PAHs. PAHs are of importance because of their ubiquity and high abundance inferred from the infrared data, and also because they may link the molecular and dust phases of the interstellar medium. A presence or absence of UV absorption bands due to PAHs could be a definitive test of this hypothesis. We should be able to detect a 20 Å wide feature down to a 3 limit of $0.02 A V . No such absorption features are seen other than the well-known 2175 Å bump.
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.
Laboratory Infrared Spectroscopy of Cationic Polycyclic Aromatic Hydrocarbon Molecules
The Astrophysical Journal, 2003
Infrared spectroscopy of a variety of interstellar sources shows strong mid-IR emission bands, which are generally attributed to emission from highly vibrationally excited polycyclic aromatic hydrocarbon molecules (PAHs) in the neutral and, particularly, cationic states. Over the past decade, various experimental methods have been developed to record the infrared spectra of cationic PAHs in the laboratory. In this paper, we discuss available experimental spectra obtained with matrix isolation spectroscopy (MIS), infrared multiple-photon dissociation of trapped ions (MPD), dissociation spectroscopy of ionic PAH van der Waals clusters (VDW), and infrared emission (IRE). Moreover, we compare these experimental spectra to density functional theory (DFT) calculations. The main body of experimental data relies on MIS and MPD spectra, and we present a detailed comparison of results from these methods, providing linear and multiple-photon absorption data, respectively. The effects of multiple-photon absorption, as encountered in MPD, and multiple-photon emission, occurring in interstellar spectra, are carefully assessed with the use of mathematical models, which include the effects of vibrational anharmonicity. We show that an analysis of the multiple-photon and linear data can provide important information on the anharmonicity parameters, which is otherwise difficult to attain. This is illustrated with a detailed comparison of the linear and multiplephoton absorption spectra of the naphthalene cation, yielding experimental anharmonicity parameters for the IR-active modes in the 500-1700 cm À1 range.