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The gas phase vibrational spectroscopy of cryogenically cooled C 2  n  + 1N −  anions with  n  = 1 − 5 is investigated in the spectral range of the C≡C and C≡N stretching modes (1850–2400 cm  – 1 ) by way of infrared photodissociation (IRPD) spectroscopy of messenger-tagged C 2 n +1 N  –  ·  m D 2  complexes. The IRPD spectra are assigned based on a comparison to previously reported anharmonic and harmonic CCSD(T) vibrational frequencies and intensities. Experimentally determined and predicted anharmonic vibrational transition energies lie within ± 21 cm  – 1 . For the harmonic CCSD(T)/vqz+ vibrational frequencies a scaling factor of 0.9808 is determined, resulting in comparable absolute deviations. The influence of the D 2 -messenger molecules on the structure and the IRPD spectrum is found to be small. Compared to the results of previous IR matrix isolation studies additional, in particular weaker, IR-active transitions are identified.

Infrared Photodissociation Spectroscopy of C 2 n +1 N − Anions with n = 1 – 5