We report the observation and analysis of spectra in part of the near-infrared spectrum of C 2 H, originating in rotational levels in the ground and lowest two excited bending vibrational levels of the groundX 2 Σ + state. In the analysis, we have combined present and previously reported high resolution spectroscopic data for the lower levels involved in the transitions to determine significantly improved molecular constants to describe the fine and hyperfine split rotational levels of the radical in the zero point, v 2 = 1 and the 2 Σ + component of v 2 = 2. Two of the upper state vibronic levels involved had not been observed previously. The data and analysis indicate the electronic wavefunction character changes with bending vibrational excitation in the ground state and provide avenues for future measurements of reactivity of the radical as a function of vibrational excitation.
The pressure dependence of the OH + C2H4 addition reaction has been investigated using frequency‐modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2 to 361 Torr. The pressure‐dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high‐level ab initio calculations have identified a prereaction complex on the OH + C2H4 potential energy surface. The influence of this complex on the OH + C2H4 kinetics has been investigated using one‐dimensional master equation analyses of the current and previous experimental measurements.
Optical frequency comb-referenced measurements of self pressure-broadened line profiles of the R(8) to R(13) lines in the ν1 + ν3 combination band of acetylene near 1.52 µm are reported. The analysis of the data found no evidence for a previously reported [Iwakuni et al., Phys. Rev. Lett. 117(14), 143902 (2016)] systematic alternation in self pressure-broadened line widths with the nuclear spin state of the molecule. The present work brought out the need for the use of an accurate line profile model and careful accounting for weak background absorptions due to hot band and lower abundance isotopomer lines. The data were adequately fit using the quadratic speed-dependent Voigt profile model, neglecting the small speed-dependent shift. Parameters describing the most probable and speed-dependent pressure-broadening, most probable shift, and the line strength were determined for each line. Detailed modeling of the results of Iwakuni et al. showed that their neglect of collisional narrowing due to the speed-dependent broadening term combined with the strongly absorbing data recorded and analyzed in transmission mode were the reasons for their results.
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