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Title: Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Abstract

Singlet dihydroxycarbene (HO$$\ddot C$$OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans, trans-or trans, cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans-and trans, cis-rotamers are (μa, μb) = (0.00,0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HO$$\ddot C$$OH torsional interconversion and tautomerization barriers.

Authors:
 [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1]
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  1. Univ. of Georgia, Athens, GA (United States)
  2. Univ. of Texas at Austin, Austin, TX (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1409052
Alternate Identifier(s):
OSTI ID: 1228594
Grant/Contract Number:  
SC0008086; FG02-12ER16298
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 14; 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

Citation Formats

Broderick, Bernadette M., McCaslin, Laura, Moradi, Christopher P., Stanton, John F., and Douberly, Gary E. Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene. United States: N. p., 2015. Web. doi:10.1063/1.4917421.
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Broderick, Bernadette M., McCaslin, Laura, Moradi, Christopher P., Stanton, John F., & Douberly, Gary E. Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene. United States. https://doi.org/10.1063/1.4917421
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Broderick, Bernadette M., McCaslin, Laura, Moradi, Christopher P., Stanton, John F., and Douberly, Gary E. Tue . "Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene". United States. https://doi.org/10.1063/1.4917421. https://www.osti.gov/servlets/purl/1409052.
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@article{osti_1409052,
title = {Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene},
author = {Broderick, Bernadette M. and McCaslin, Laura and Moradi, Christopher P. and Stanton, John F. and Douberly, Gary E.},
abstractNote = {Singlet dihydroxycarbene (HO$\ddot C$OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans, trans-or trans, cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans-and trans, cis-rotamers are (μa, μb) = (0.00,0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HO$\ddot C$OH torsional interconversion and tautomerization barriers.},
doi = {10.1063/1.4917421},
journal = {Journal of Chemical Physics},
number = 14,
volume = 142,
place = {United States},
year = {Tue Apr 14 00:00:00 EDT 2015},
month = {Tue Apr 14 00:00:00 EDT 2015}
}
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