Theoretical study of infrared spectra of interstellar PAH molecules with N, NH & NH$_2$ incorporation

TL;DR

This study uses density functional theory to analyze how nitrogen incorporation in PAH molecules affects their infrared spectra, providing insights into their potential roles in explaining Unidentified Infrared bands in space.

Contribution

It presents the first detailed theoretical analysis of N, NH, and NH2 incorporation effects on PAH IR spectra, linking molecular structure to astronomical IR observations.

Findings

Neutral N-containing PAHs can produce IR bands similar to ionized PAHs.

N incorporation affects the 6.2 and 11.2 μm band ratios, challenging their use as ionization indicators.

N at the periphery may form N-H bonds, producing features near 2.9–3.0 μm, yet these are not observed.

Abstract

This work presents theoretical calculations of infrared spectra of nitrogen (N)-containing polycyclic aromatic hydrocarbon (PAH) molecules with incorporation of N, NH and NH$_2$ using density functional theory (DFT). The properties of their vibrational modes in 2--15 $\mu \rm m$ are investigated in relation to the Unidentified Infrared (UIR) bands. It is found that neutral PAHs, when incorporated with NH$_2$ and N (at inner positions), produce intense infrared bands at 6.2, 7.7 and 8.6 $\mu \rm m$ that have been normally attributed to ionized PAHs so far. The present results suggest that strong bands at 6.2 and 11.2 $\mu \rm m$ can arise from the same charge state of some N-containing PAHs, arguing that there might be some N-abundant astronomical regions where the 6.2 to 11.2 $\mu \rm m$ band ratio is not a direct indicator of PAHs' ionization. PAHs with NH$_2$ and N inside the carbon structure show the UIR band features characteristic to star-forming regions as well as reflection nebulae (Class A), whereas PAHs with N at the periphery have similar spectra to the UIR bands seen in planetary nebulae and post-AGB stars (Class B). The presence of N atom at the periphery of a PAH may attract H or H$^{+}$ to form N-H and N-H$_2$ bonds, exhibiting features near 2.9--3.0 $\mu \rm m$, which are not yet observationally detected. The absence of such features in the observations constrains the contribution of NH and NH$_2$ substituted PAHs that could be better tested with concentrated observations in this range. However, PAHs with N without H either at the periphery or inside the carbon structure do not have the abundance constraint due to the absence of 2.9--3.0 $\mu \rm m$ features and are relevant in terms of positions of the UIR bands. Extensive theoretical and experimental studies are required to obtain deeper insight.