Sub-Doppler infrared spectroscopy and formation dynamics of triacetylene in a slit supersonic expansion

Infrared spectroscopy and formation dynamics of triacetylene are investigated in a slit jet supersonic discharge and probed with sub-Doppler resolution (≈60 MHz) on the fundamental antisymmetric CH stretch mode (ν5). The triacetylene is generated in the throat of the discharge by sequential attack of ethynyl radical with acetyelene and diacetylene: (i) HCCH → HCC + H, (ii) HCC + HCCH → HCCCCH + H, (iii) HCC + HCCCCH → HCCCCCCH + H, cooled rapidly in the slit expansion to 15 K, and probed by near shot-noise-limited absorption sensitivity with a tunable difference-frequency infrared laser. The combination of jet cooled temperatures (Trot = 15 K) and low spectral congestion permits (i) analysis of rotationally avoided crossings in the ν5 band ascribed to Coriolis interactions, as well as (ii) first detection of ν5 Π-Π hot band progressions built on the ν12 sym CC bend and definitively assigned via state-of-the-art ab initio vibration-rotation interaction parameters (αi), which make for interesting comparison with recent spectroscopic studies of Doney et al. [J. Mol. Spectrosc. 316, 54 (2015)]. The combined data provide direct evidence for significantly non-equilibrium populations in the CC bending manifold, dynamically consistent with a strongly bent radical intermediate and transition states for forming triacetylene product. The presence of intense triacetylene signals under cold, low density slit jet conditions provides support for (i) barrierless addition of HCC with HCCCCH and (ii) a high quantum yield for HCCCCCCH formation. Complete basis set calculations for energetics [CCSD(T)-f12/VnZ-f12, n = 2,3] and frequencies [CCSD(T)-f12/VdZ-f12] are presented for both radical intermediate and transition state species, predicting collision stabilization in the slit jet expansion to be competitive with unimolecular decomposition with increasing polyyne chain length.