The 6.2 μm PAH Feature and the Role of Nitrogen: Revisited

Abstract

Abstract This study revisits the role that nitrogen inclusion in polycyclic aromatic hydrocarbons (PAHs; those with nitrogen inclusion, PANHs) plays in their infrared (IR) spectral properties. We present spectra of pure PAHs, PANHs, and protonated PANHs, computed using density functional theory and basis sets that treat polarization. We investigate trends in peak position and relative intensities as a function of nitrogen position, charge, and geometry. We use Spitzer-IRS spectral map data of the northwest photodissociation region of NGC 7023 and a database-fitting approach, using exclusively the PA(N)H spectra computed in this paper, to assess their IR contribution to the cosmic PAH emission. We find that, by including the treatment of polarization, pure PAH cations can account for the class A 6.2 μm PAH emission, with the 6.2 μm band position being dependent on the molecular geometry. PANH cations are required to reproduce the most blueshifted 6.2 μm bands observed in class A sources, albeit PANH cations come with strong 11.0 μm emission. Blind database fits demonstrate that the restriction imposed by the 11.0 μm emission in the astronomical spectra limits the contribution of PANH cations and the fits have to use neutral PANHs to avoid inflating the 11.0 μm feature even further. By assuming that all of the 11.0 μm emission is due to PANHs, we derive an upper limit for the contribution of PANH cations to the astronomical 6.2 μm PAH band of ∼12%. The fits further show hydrogenated PANHs significantly contributing in NGC 7023's more benign region, supporting the view that shielded environments could sustain protonated PA(N)Hs.