A Near-Threshold Shape Resonance in the Valence-Shell Photoabsorption of Linear Alkynes

Jacovella, U.; Holland, D. M.  P.; Boyé-Péronne, S.; Gans, Bérenger; de Oliveira, N.; Ito, K.; Joyeux, D.; Archer, L. E.; Lucchese, R. R.; Xu, Hong; Pratt, S. T.

doi:10.1021/acs.jpca.5b06949

Title: A Near-Threshold Shape Resonance in the Valence-Shell Photoabsorption of Linear Alkynes

Journal Article · Thu Dec 17 00:00:00 EST 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b06949· OSTI ID:1391875

Jacovella, U.; Holland, D. M. P.; Boyé-Péronne, S.; Gans, Bérenger; de Oliveira, N.; Ito, K.; Joyeux, D.; Archer, L. E.; Lucchese, R. R.; Xu, Hong; Pratt, S. T.

The room-temperature photoabsorption spectra of a number of linear alkynes with internal triple bonds (e.g., 2-butyne, 2-pentyne, and 2- and 3-hexyne) show similar resonances just above the lowest ionization threshold of the neutral molecules. These features result in a substantial enhancement of the photoabsorption cross sections relative to the cross sections of alkynes with terminal triple bonds (e.g., propyne, 1-butyne, 1-pentyne,...). Based on earlier work on 2-butyne [Xu et al., J. Chem. Phys. 2012, 136, 154303], these features are assigned to excitation from the neutral highest occupied molecular orbital (HOMO) to a shape resonance with g (l = 4) character and approximate pi symmetry. This generic behavior results from the similarity of the HOMOs in all internal alkynes, as well as the similarity of the corresponding g pi virtual orbital in the continuum. Theoretical calculations of the absorption spectrum above the ionization threshold for the 2- and 3-alkynes show the presence of a shape resonance when the coupling between the two degenerate or nearly degenerate pi channels is included, with a dominant contribution from l = 4. These calculations thus confirm the qualitative arguments for the importance of the l = 4 continuum near threshold for internal alkynes, which should also apply to other linear internal alkynes and alkynyl radicals. The 1-alkynes do not have such high partial waves present in the shape resonance. The lower l partial waves in these systems are consistent with the broader features observed in the corresponding spectra.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1391875

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 50; ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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