High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

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

doi:10.1063/1.4926541

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

Journal Article · Thu Jul 16 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4926541· OSTI ID:1396007

Jacovella, U. ^[1]; Holland, D. M. P. ^[2]; Boyé-Péronne, S. ^[3]; Gans, B. ^[3]; de Oliveira, N. ^[4]; Joyeux, D. ^[4]; Archer, L. E. ^[4]; Lucchese, R. R. ^[5]; Xu, H. ^[6]; Pratt, S. T. ^[6]

ETH Zürich (Switzerland). Lab. für Physikalische Chemie
Daresbury Lab. (United Kingdom)
National Centre for Scientific Research (CNRS), Orsay (France)
Synchrotron Soleil (France)
Texas A & M Univ., College Station, TX (United States)
Argonne National Laboratory, Argonne, Illinois 60439, USA

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. We believe this type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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

OSTI ID:: 1396007

Alternate ID(s):: OSTI ID: 1228676
OSTI ID: 22489727

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 143; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical elements
Fourier transform spectroscopy
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Oscillator strengths
Photoabsorption
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Rydberg states
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High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

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