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Title: The effects of methyl internal rotation and {sup 14}N quadrupole coupling in the microwave spectra of two conformers of N,N-diethylacetamide

The gas phase structures and internal dynamics of N,N-diethylacetamide were determined with very high accuracy using a combination of molecular beam Fourier-transform microwave spectroscopy and quantum chemical calculations at high levels. Conformational studies yielded five stable conformers with C{sub 1} symmetry. The two most energetically favorable conformers, conformer I and II, could be found in the experimental spectrum. For both conformers, quadrupole hyperfine splittings of the {sup 14}N nucleus and torsional fine splittings due to the internal rotation of the acetyl methyl group occurred in the same order of magnitude and were fully assigned. The rotational constants, centrifugal distortion constants as well as the quadrupole coupling constants of the {sup 14}N nucleus were determined and fitted to experimental accuracy. The V{sub 3} potentials were found to be 517.04(13) cm{sup −1} and 619.48(91) cm{sup −1} for conformer I and II, respectively, and compared to the V{sub 3} potentials found in other acetamides. Highly accurate CCSD(T) and DMC calculations were carried out for calculating the barriers to internal rotation in comparison with the experimentally deduced V{sub 3} values.
Authors:
; ; ; ;  [1]
  1. Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074 Aachen (Germany)
Publication Date:
OSTI Identifier:
22413242
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 20; Other Information: (c) 2014 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; ACCURACY; ACETAMIDE; COUPLING CONSTANTS; FOURIER TRANSFORMATION; MICROWAVE RADIATION; MICROWAVE SPECTRA; MOLECULAR BEAMS; NITROGEN 14; ROTATION; SPECTROSCOPY