The Journal of chemical physics

Electronic spectra of oxygen containing polycyclic hydrocarbon cations and the protonated analogues.

PMID 26328848


The electronic transitions of 9-fluorenone FL(+) and 2,3,6,7-dibenzotropone DBT(+) cations were detected in 6 K neon matrices following a mass-selective deposition. The absorptions at 649.2 and 472.2 nm are assigned to the 2 (2)B1←X̃(2)A2 FL(+) and 2(2)A(')←X̃(2)A(') DBT(+) transitions. Absorption spectra of protonated 9-fluorenone H(+)-FL and 2,3,6,7-dibenzotropone H(+)-DBT have also been measured. Protonation of the oxygenated polycyclic aromatic hydrocarbons is carried out in a hot cathode source via in situ produced protonated ethanol. Vibrationally resolved absorptions commencing at 423.3 nm of H-FL(+) and two band systems of H-DBT(+) with origins at 502.4 and 371.5 nm are assigned to the 2(1)A(')←X̃(1)A(') electronic transition of 9-hydroxy-fluorenyl cation and 1 (1)A←X̃(1)A, 2 (1)A←X̃(1)A of 2,3,6,7-dibenzocycloheptenol cation. The assignments are based on vertical excitation energy calculations with time dependent density functional theory, symmetry adapted cluster configuration interaction, and MS-CASPT2 methods.