The electronic spectrum of the methyl propargyl cation (2-butyn-1-yl cation, H2C4H3+) is measured over the 230–270 nm range by photodissociating the bare cation and its Ar and N2 tagged complexes in a tandem mass spectrometer. The observed A1A1 band system has an origin at 37 753 cm−1 for H2C4H3+, 37738 cm−1 for H2C4H3+—Ar, and 37 658 cm−1 for H2C4H3+N2. The methyl propargyl cation photodissociates to produce either C2H3++C2H2 (protonated acetylene + acetylene) or H2C4H++H2 (protonated diacetylene + dihydrogen). Photodissociation spectra of H2C4H3+, H2C4H3+—Ar, and H2C4H3+N2 exhibit similar vibronic structure, with a strong progression of spacing 630 cm−1 corresponding to excitation of the C—C stretch mode. Interpretation of the spectra is aided by ground and excited state calculations using time dependent density functional theory at the ωB97X-D/aug-cc-pVDZ level of theory. Ab initio calculations and master equation simulations were used to interpret the dissociation of H2C4H3+ on the ground state manifold. These calculations support the experimentally observed product branching ratios in which acetylene elimination dominates and also suggests that channel switching occurs at higher energies to favor H2 elimination.

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