The abundances of hydrocarbon functional groups in the interstellar medium inferred from laboratory spectra of hydrogenated and methylated polycyclic aromatic hydrocarbons

TL;DR

This study uses laboratory IR spectra and molecular analysis to estimate the abundance of hydrocarbon functional groups in interstellar PAHs, revealing variations across different cosmic environments and implications for IR emission features.

Contribution

It provides the first detailed laboratory-based quantification of hydrocarbon functional groups in interstellar PAHs, linking molecular structure to IR spectral features.

Findings

Aliphatic CHx groups contribute significantly to the 3.4 μm feature.

Aromatic =CH groups are scarce in some lines of sight.

Heavy hydrogenation is unlikely in typical astronomical IR sources.

Abstract

Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH3), methylene (>CH2), 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, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Supported by calculations at the density functional theory level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium at 3.4 mu-m and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CHx groups (x = 1,2,3) would contribute approximately in equal quantities to the 3.4 mu-m feature (N_{CHx} / N_{H} approx 10^{-5} - 2 * 10^{-5}). The abundances, however, may be two to four times lower if a major contribution to the 3.4 mu-m 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, >CH2 groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star.