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

Singlet dihydroxycarbene (HOC{sup ¨}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 (μ{sub a}, μ{sub b}) = (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 HOC{sup ¨}OH torsional interconversion and tautomerization barriers.
Authors:
; ;  [1] ; ;  [2]
  1. Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556 (United States)
  2. Department of Chemistry, University of Texas at Austin, Austin, Texas 78712 (United States)
Publication Date:
OSTI Identifier:
22415640
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCULATION METHODS; COMPARATIVE EVALUATIONS; DIPOLES; ELECTRIC DIPOLE MOMENTS; ELECTRONIC STRUCTURE; HELIUM; HELIUM 4; INFRARED SPECTRA; LASER SPECTROSCOPY; OXALIC ACID; PROBES; PYROLYSIS; SPIN; SYMMETRY