Anharmonicity and the IR Emission Spectrum of Neutral Interstellar PAH Molecules

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-05, Vol.126 (20), p.3198-3209
• Main Authors: Mackie, Cameron J., Candian, Alessandra, Lee, Timothy J., Tielens, Alexander G. G. M.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c01849

The characteristics of the CH stretching and out-of-plane bending modes in polycyclic aromatic hydrocarbon molecules are investigated using anharmonic density functional theory (DFT) coupled to a vibrational second-order perturbation treatment taking resonance effects into account. The results are used to calculate the infrared emission spectrum of vibrationally excited species in the collision-less environment of interstellar space. This model follows the energy cascade as the molecules relax after the absorption of a UV photon in order to calculate the detailed profiles of the infrared bands. The results are validated against elegant laboratory spectra of polycyclic aromatic hydrocarbon absorption and emission spectra obtained in molecular beams. The factors which influence the peak position, spectral detail, and relative strength of the CH stretching and out-of-plane bending modes are investigated, and detailed profiles for these modes are derived. These are compared to observations of astronomical objects in space, and the implications for our understanding of the characteristics of the molecular inventory of space are assessed.