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

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

doi:10.1021/acs.jpca.5b06949

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

Journal Article · Thu Oct 15 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b06949· OSTI ID:1461973

Jacovella, U. ^[1]; Holland, D. M. P. ^[2]; Boye-Peronne, S. ^[3]; Gans, Berenger ^[3]; de Oliveira, N. ^[4]; Ito, K. ^[4]; Joyeux, D. ^[4]; Archer, L. E. ^[4]; Lucchese, R. R. ^[5]; Xu, Hong ^[6]; Pratt, S. T. ^[6]

Swiss Federal Inst. of Technology in Zurich (ETH Zurich) (Switzerland). Lab. of Physical Chemistry
Science and Technology Facilities Council (STFC), Daresbury (United Kingdom). Daresbury Lab.
National Centre for Scientific Research (CNRS) and Univ. of Paris-Sud, Orsay (France). Inst. of Molecular Sciences of Orsay (ISMO)
Synchrotron SOLEIL, Gif-sur-Yvette (France)
Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States)

In this paper, 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 π symmetry. This generic behavior results from the similarity of the HOMOs in all internal alkynes, as well as the similarity of the corresponding gπ 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 π 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. Finally, the lower l partial waves in these systems are consistent with the broader features observed in the corresponding spectra.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Robert A. Welch Foundation (United States); Science and Technology Facilities Council (STFC) (United Kingdom)

Grant/Contract Number:: AC02-06CH11357; SC0012198

OSTI ID:: 1461973

Alternate ID(s):: OSTI ID: 1391875

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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