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Title: {sup 33}S hyperfine interactions in H{sub 2}S and SO{sub 2} and revision of the sulfur nuclear magnetic shielding scale

Using the Lamb-dip technique, the hyperfine structure in the rotational spectra of H{sub 2}{sup 33}S and {sup 33}SO{sub 2} has been resolved and the corresponding parameters—that is, the sulfur quadrupole-coupling and spin–rotation tensors—were determined. The experimental parameters are in good agreement with results from high-level coupled-cluster calculations, provided that up to quadruple excitations are considered in the cluster operator, sufficiently large basis sets are used, and vibrational corrections are accounted for. The {sup 33}S spin-rotation tensor for H{sub 2}S has been used to establish a new sulfur nuclear magnetic shielding scale, combining the paramagnetic part of the shielding as obtained from the spin–rotation tensor with a calculated value for the diamagnetic part as well as computed vibrational and temperature corrections. The value of 716(5) ppm obtained in this way for the sulfur shielding of H{sub 2}S is in good agreement with results from high-accuracy quantum-chemical calculations but leads to a shielding scale that is about 28 ppm lower than the one suggested previously in the literature, based on the {sup 33}S spin-rotation constant of OCS.
Authors:
 [1] ;  [2] ; ;  [3]
  1. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, N-0315 Oslo (Norway)
  2. Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)
  3. Dipartimento di Chimica “Giacomo Ciamician,” Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy)
Publication Date:
OSTI Identifier:
22253233
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 24; Other Information: (c) 2013 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; HYDROGEN; HYDROGEN SULFIDES; HYPERFINE STRUCTURE; INTERACTIONS; MAGNETIC SHIELDING; PARAMAGNETISM; SPECTRA; SPIN; SULFUR; SULFUR 33; SULFUR DIOXIDE; TENSORS