Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups: Intensity Scaling for the C–H Stretching Modes and Astrophysical Implications

Journal Article · Fri Mar 10 04:00:00 EST 2017 · Astrophysical Journal

DOI:https://doi.org/10.3847/1538-4357/AA5FA9· OSTI ID:22869218

Yang, X. J.; Zhong, J. X. ^[1]; Li, Aigen ^[2]

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1. Department of Physics, Xiangtan University, 411105 Xiangtan, Hunan Province (China)
2. Department of Physics and Astronomy, University of Missouri, Columbia, MO 65211 (United States)

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 knowledge of the intrinsic oscillator strengths of the 3.3 μm aromatic C–H stretch (A{sub 3.3}) and the 3.4 μm aliphatic C–H stretch (A{sub 3.4}). Lacking experimental data on A{sub 3.3} and A{sub 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 those 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 that (I{sub 3.4}/I{sub 3.3}){sub 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 relation for determining the aliphatic fraction of the UIE carriers (i.e., the ratio of the number of C atoms in aliphatic units N{sub C,ali} to that in aromatic rings N{sub C,aro}) from the observed band ratios (I{sub 3.4}/I{sub 3.3}){sub obs}: N{sub C,ali}/N{sub C,aro}≈0.57×(I{sub 3.4}/I{sub 3.3}){sub obs} for neutrals and N{sub C,ali}/N{sub C,aro}≈0.26×(I{sub 3.4}/I{sub 3.3}){sub obs} for cations.

• OSTI ID: 22869218
• Journal Information: Astrophysical Journal, Journal Name: Astrophysical Journal Journal Issue: 2 Vol. 837; ISSN ASJOAB; ISSN 0004-637X
• Country of Publication: United States
• Language: English

Related Subjects

79 ASTRONOMY AND ASTROPHYSICS
ASTROPHYSICS
ATOMS
COSMIC DUST
DENSITY FUNCTIONAL METHOD
DETECTION
EMISSION
MOLECULES
OSCILLATOR STRENGTHS
PERTURBATION THEORY
POLYCYCLIC AROMATIC HYDROCARBONS
SCALING
SPECTRA