CN stretches around 4.4 microns dominate the IR absorption spectra of cyano-polycyclic aromatic hydrocarbons

Anharmonic quantum chemical computations reveal a strong, narrow (width = 0.075 μm) band in the 4.3–4.5 μm region of the absorption spectra of the cyano-substituted polycyclic aromatic hydrocarbons (CN-PAHs) cyanonaphthalene, cyanoanthracene, cyanophenanthrene, and cyanopyrene. This narrow window with intense IR lines implies that CN-PAHs of various shapes and sizes offer little variation in both wavelength and intensity in this region. Subsequently, this band can be used as a tracer for CN-PAHs. The distinct features making up the band are assigned to mixed vibrational states consisting of the CN stretch fundamental and various combination bands, including in-plane CH bends, CC skeletal bends, and CC skeletal breathing motions. The extraordinarily large intrinsic intensity of the fundamental CN stretch is redistributed to nearby states via anharmonic coupling, which is readily captured when using second order vibrational perturbation theory with resonance polyad matrices. This redistribution of intensity leads to a complex spectrum. The intense bands in this wavelength region may contribute to the baseline continuum and undulating macroscopic structure seen in recent JWST NIRSpec observations.