The IRAM-30m line survey of the Horsehead PDR: III. High abundance of complex (iso-)nitrile molecules in UV-illuminated gas

Complex (iso-)nitrile molecules, such as CH3CN and HC3N, are relatively easily detected in our Galaxy and in other galaxies. We constrain their chemistry through observations of two positions in the Horsehead edge: the photo-dissociation region (PDR) and the dense, cold, and UV-shielded core just behind it. We systematically searched for lines of CH3CN, HC3N, C3N, and some of their isomers in our sensitive unbiased line survey at 3, 2, and 1mm. We derived column densities and abundances through Bayesian analysis using a large velocity gradient radiative transfer model. We report the first clear detection of CH3NC at millimeter wavelength. We detected 17 lines of CH3CN at the PDR and 6 at the dense core position, and we resolved its hyperfine structure for 3 lines. We detected 4 lines of HC3N, and C3N is clearly detected at the PDR position. We computed new electron collisional rate coefficients for CH3CN, and we found that including electron excitation reduces the derived column density by 40% at the PDR position. While CH3CN is 30 times more abundant in the PDR than in the dense core, HC3N has similar abundance at both positions. The isomeric ratio CH3NC/CH3CN is 0.15+-0.02. In the case of CH3CN, pure gas phase chemistry cannot reproduce the amount of CH3CN observed in the UV-illuminated gas. We propose that CH3CN gas phase abundance is enhanced when ice mantles of grains are destroyed through photo-desorption or thermal-evaporation in PDRs, and through sputtering in shocks. (abridged)