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

Abstract

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.

Authors:
 [1];  [2];  [3];  [3];  [4];  [4];  [4];  [5];  [6];  [6]
+ Show Author Affiliations
  1. ETH Zürich (Switzerland). Lab. für Physikalische Chemie
  2. Daresbury Lab. (United Kingdom)
  3. National Centre for Scientific Research (CNRS), Orsay (France)
  4. Synchrotron Soleil (France)
  5. Texas A & M Univ., College Station, TX (United States)
  6. Argonne National Laboratory, Argonne, Illinois 60439, USA
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1396007
Alternate Identifier(s):
OSTI ID: 1228676
Grant/Contract Number:  
AC02-06CH11357; SC0012198
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Fourier transform spectroscopy; Synchrotrons; Chemical elements; Rydberg states; Vacuum ultraviolet radiation; Operator theory; Quantum chemical calculations; Rydberg series; Photoabsorption; Oscillator strengths

Citation Formats

Jacovella, U., Holland, D. M. P., Boyé-Péronne, S., Gans, B., de Oliveira, N., Joyeux, D., Archer, L. E., Lucchese, R. R., Xu, H., and Pratt, S. T. High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne. United States: N. p., 2015. Web. doi:10.1063/1.4926541.
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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. High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne. United States. https://doi.org/10.1063/1.4926541
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Jacovella, U., Holland, D. M. P., Boyé-Péronne, S., Gans, B., de Oliveira, N., Joyeux, D., Archer, L. E., Lucchese, R. R., Xu, H., and Pratt, S. T. Thu . "High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne". United States. https://doi.org/10.1063/1.4926541. https://www.osti.gov/servlets/purl/1396007.
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@article{osti_1396007,
title = {High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne},
author = {Jacovella, U. and Holland, D. M. P. and Boyé-Péronne, S. and Gans, B. and de Oliveira, N. and Joyeux, D. and Archer, L. E. and Lucchese, R. R. and Xu, H. and Pratt, S. T.},
abstractNote = {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.},
doi = {10.1063/1.4926541},
journal = {Journal of Chemical Physics},
number = 3,
volume = 143,
place = {United States},
year = {Thu Jul 16 00:00:00 EDT 2015},
month = {Thu Jul 16 00:00:00 EDT 2015}
}
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https://doi.org/10.1063/1.4926541
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