Gas-Phase Vibrational Spectroscopy of the Hydrocarbon Cations l-C₃H⁺, HC₃H⁺, and c-C₃H₂⁺: Structures, Isomers, and the Influence of Ne-Tagging.

ABSTRACT: We report the first gas-phase vibrational spectra of the hydrocarbon ions C₃H⁺ and C₃H₂⁺. The ions were produced by electron impact ionization of allene. Vibrational spectra of the mass-selected ions tagged with Ne were recorded using infrared predissociation spectroscopy in a cryogenic ion trap instrument using the intense and widely tunable radiation of a free electron laser. Comparison of high-level quantum chemical calculations and resonant depletion measurements revealed that the C₃H⁺ ion is exclusively formed in its most stable linear isomeric form, whereas two isomers were observed for C₃H₂⁺. Bands of the energetically favored cyclic c-C₃H₂⁺ are in excellent agreement with calculated anharmonic frequencies, whereas for the linear open-shell HCCCH⁺ (²?_g) a detailed theoretical description of the spectrum remains challenging because of Renner-Teller and spin-orbit interactions. Good agreement between theory and experiment, however, is observed for the frequencies of the stretching modes for which an anharmonic treatment was possible. In the case of linear l-C₃H⁺, small but non-negligible effects of the attached Ne on the ion fundamental band positions and the overall spectrum were found.

SUBMITTER: Brunken S 

PROVIDER: S-EPMC6755619 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature