2003ApJ...594..869P

We report B-LYP/6-31G* and B3-LYP/6-31G* density functional theory calculations on a set of polycyclic hydrocarbons, ranging in size from C₁₉H₂₂to C₃₆H₃₂, combining aromatic (unsaturated) and aliphatic (saturated, sp³-hybridized carbon) ring systems. These locally aromatic polycyclic hydrocarbons (LAPHs), generally exhibiting large deviations from planarity, may be considered as intermediate structures between polycyclic aromatic hydrocarbons (PAHs) and nanodiamonds. Calculated infrared vibrational frequencies are found to be similar to those observed experimentally in spectra of hydrogenated amorphous carbon (HAC) and other carbonaceous solids. In the C-H stretching region (∼3.1-3.6 µm) these species are characterized by strong absorption/emission within both the aliphatic and aromatic C-H bands. They also show spectral features associated with tertiary C-H. Similar features are evident in calculated spectra of the corresponding ions, which we have characterized in some cases. Ionization results in the particular enhancement of a spectral feature typically seen at ∼6.4 µm, in the aromatic C-C stretching region. In keeping with previous experimental and theoretical studies on the spectra of neutral and cationic PAHs, we find that the influence of ionization on the relative intensities of C-C and C-H stretching features is much greater than the influence of molecular structure. We suggest that LAPHs may be significant contributors to emission in Type B unidentified infrared emission sources.