Journal of Physical Chemistry A, Vol.116, No.17, 4323-4329, 2012
Electronic Spectra of Gas-Phase Polycyclic Aromatic Nitrogen Heterocycle Cations: Isoquinoline(+) and Quinoline(+)
Electronic spectra of the gas-phase isoquinoline(+)-Ar and quinoline(+)-Ar complexes are recorded using photodissociation spectroscopy by monitoring the Ar loss channel. The D-3 <- D-0 and D-4 <- D-0 band origins for isoquinoline(+)-Ar are observed at 15245 +/- 15 cm(-1) and 21960 +/- 15 cm(-1), respectively, whereas for quinoline(+)-Ar they appear at 16050 +/- 15 cm(-1) and 21955 +/- 15 cm(-1), respectively. Strong vibronic progressions for the D-3 <- D-0 band systems of both isoquinoline(+)-Ar and quinoline(+)-Ar are modeled and assigned in terms of ring deformation and carbon carbon stretch vibrational modes using time-dependent density functional theory calculations in conjunction with Franck-Condon simulations. The properties of the isoquinoline(+) and quinoline(+) molecules are compared with those of the isoelectronic naphthalene(+) molecule. The existence of strong progressions in the visible spectra of isoquinoline(+)-Ar and quinoline(+)-Ar suggests that the corresponding isoquinoline(+) and quinoline(+) molecular cations are unlikely to be responsible for diffuse interstellar bands.