QUIJOTE discovery of the cation radicals HC₅N⁺and HC₇N⁺

We present the discovery with the QUIJOTE line survey of the cations HC5N+ and HC7N+ in the direction of TMC-1. Seven lines with half-integer quantum numbers from J = 25/2 23/2 to 37/2 35/2 have been assigned to HC5N+ and eight lines from J = 55/2 53/2 to 71/2 69/2 to HC7N+. Both species have inverted 2? ground electronic states with very good estimates for their B0 and ASO constants based on optical observations. The lines with the lowest J of HC5N+ exhibit multiple components due to the hyperfine structure introduced by the H and N nuclei. However, these different components collapse for the higher J. No hyperfine structure is found for any of the lines of HC7N+. The derived effective rotational and distortion constants for HC5N+ are Beff = 1336.662 ± 0.001 MHz and Deff = 27.4 ± 2.6 Hz, while for HC7N+ they are Beff = 567.85036 ± 0.00037 MHz and Deff = 4.01 ± 0.19 Hz. From the observed intensities, we derived Trot = 5.5 ± 0.5 K and N = (9.9 ± 1.0) × 1010 cm-2 for HC5N+, while we obtained Trot = 8.5 ± 0.5 K and N = (2.3 ± 0.2) × 1010 cm-2 for HC7N+. The HC5N/HC5N+, C5N/HC5N+, C5N-/HC5N+, HC7N/HC7N+, HC5N+/HC7N+, and C7N-/HC7N+ abundance ratios are 670 ± 80, 4.8 ± 0.8, 1.2 ± 0.2, 1000 ± 150, 4.2 ± 0.5, and 2.2 ± 0.2, respectively. We have run chemical modelling calculations to investigate the formation and destruction of these new cations. We find that these species are mainly formed through the reactions of H2 and the cations C5N+ and C7N+, and by the reactions of H+ with HC5N and HC7N, while they are mostly destroyed through a reaction with H2 and a dissociative recombination with electrons.