Cyano-substituted polycyclic aromatic
hydrocarbons (CN-PAHs) may
contribute to the emission detected in the 7−9 μm (1430−1100
cm−1) and 11−15 μm (900−670
cm−1) regions of astronomical IR spectra. Anharmonic
quantum chemical computations of 14 CN-PAH isomers for 4 small PAHs
and benzene reveal strong, broad absorption features across the entire
300−6200 cm−1 (33−1.6 μm) frequency
range. In particular, when an full width at half maximum (fwhm) of
15 cm−1 is applied, the composite CN-PAH spectrum
greatly overlaps with the unsubstituted-PAH spectrum across the entire
300−6200 cm−1 range besides the 2200−2500
cm−1 region that arises from the strong CN stretch
fundamental of CN-PAHs and is addressed in a separate publication.
At high resolution, however, the infrared absorption spectra reveal
unique, identifiable features of CN-PAHs in the 700−950, 1100−1300,
2000−2500, and 3400−3600 cm−1 ranges.
The in-plane and out-of-plane CH bending vibrational frequencies of
CN-PAHs are shifted when comparing isomers and their unsubstituted
counterparts, making their differentiation in mixed laboratory experiments
possible. The overall aromatic CH stretch fundamental (2950−3200
cm−1) and first overtone (5950−6200 cm−1) regions are relatively unaffected by the cyano-substitution,
with changes only to the frequency range covered by, and the intensity
of, the bands. Detailed spectroscopic data on the normal mode components
of each state reported herein provide the means to directly assign
future laboratory spectra and to guide direct IR observations of astronomical
regions with, e.g., James Webb Space Telescope (JWST).