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Title:MICROWAVE SPECTRUM AND THEORETICAL INVESTIGATION OF TRIFLUOROACETIC SULFURIC ANHYDRIDE
Author(s):Huff, Anna
Contributor(s):Leopold, Ken; Smith, CJ; Mackenzie, Becca
Subject(s):Small molecules
Abstract:Trifluoroacetic sulfuric anhydride, CF$_{3}$COOSO$_{2}$OH, has been produced under supersonic jet conditions from the reaction of sulfur trioxide and trifluoroacetic acid. The rotational spectra for both the parent and deuterated isotopologues have been recorded, but were notably weaker than similar spectra obtained for other carboxylic sulfuric anhydrides. The spectra were readily fit to a Watson A-reduced Hamiltonian with no evidence of internal rotation. M06-2X/6-311++G(3df,3pd) calculations indicate that the formation of CF$_{3}$COOSO$_{2}$OH proceeds through a $\pi$$_{2}$ + $\pi$$_{2}$ + $\sigma$$_{2}$ cycloaddition mechanism analogous to that previously established for other carboxylic sulfuric anhydrides. The barrier to formation for CF$_{3}$COOSO$_{2}$OH calculated at the CCSD(T)/CBS(D-T) level is slightly positive (~0.7 kcal/mol), in contrast to the slightly negative value obtained for the formation of its acetic acid analog (acetic sulfuric anhydride). The possible role of internal rotation in the formation of both systems will be discussed.
Issue Date:06/20/18
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/100572
DOI:10.15278/isms.2018.WH06
Other Identifier(s):WH06
Date Available in IDEALS:2018-08-17
2018-12-12


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