Photoionization of the Propargyl Radical Using the R-Matrix Method

The absolute photoionization cross section of the propargyl radical measured by Savee et al. J. Chem. Phys. 2012, 136, 134307 is about 2–3 times larger than the experimental result from Robinson et al. J. Chem. Phys. 2003, 119, 5311. Meanwhile, there is a significant discrepancy in the shapes of the propargyl photoionization spectra between these two measurements and the result measured by Zhang et al. J. Chem. Phys. 2006, 124, 074302. To estimate the accuracy of the various results, we carried out comprehensive calculations with the multichannel R-matrix method, which uses multiconfigurational wave functions to generate accurate initial and final states. Three scattering models including static-exchange, correlated 1 state, and 80 state close-coupling (CC) approximations are employed to reveal the dynamic interaction. The autoionization peaks near the ionization threshold are predicted for the first time. Two resonances are detected with the photon energy around 41.4 and 49.6 eV in the 80 state CC model. We checked the sensitivity of the results to change descriptions of the active spaces, the different partial waves, and the R-matrix radii in the theoretical model. Our best results are compared with the experimental measurements, and discussions are provided. The cross sections and asymmetry parameters for the valence orbitals are reported for photon energies from ionization thresholds of 70 eV.