Anharmonic Infrared Emission of Cyano-Substituted Polycyclic Aromatic Hydrocarbon Molecules: Cyanonaphthalenes as a Case Study
Recent detections of cyano-substituted polycyclic aromatic hydrocarbons (cyano-PAHs) highlight them as key tracers of nitrogen heterocycles in the interstellar medium (ISM). However, their infrared (IR) identification requires anharmonic vibrational radiative models that account for dynamic cooling across diverse environments. We provide IR cascade emission spectra for neutral, cationic, and anionic 1- and 2-cyanonaphthalene (1- and 2-CNN) under representative astrophysical conditions, investigating how charge states and substitution positions modulate anharmonic profiles and energy redistribution during IR cascades. Using B3LYP/N07D with Second-order Vibrational Perturbation Theory (VPT2), we computed anharmonic properties and applied an optimized microcanonical sampling algorithm to calculate vibrational density of states and model environment-dependent cascade spectra. Results show that charge states strongly tune the CN nitrile band: anion intensity is enhanced by an order of magnitude compared to neutrals, whereas cation intensity is slightly weaker. 1- and 2-CNN present distinct isomeric signatures: 1-CNN displays a complex "red-wing" structure in the 3.3-micron C-H stretch due to peri-hydrogen interactions, whereas 2-CNN yields a more symmetric profile. We evaluated the fractional energy emitted via the CN stretch relative to total cascade emissivity across charge states and environments. Combined with observed CN fluxes, these fractions provide a quantitative tool to constrain cyano-PAH abundances. By bridging laboratory benchmarks with dynamic interstellar emission, this work delivers accurate anharmonic fingerprints to guide JWST observational analysis.