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Title: Trends in alkali metal hydrosulfides: A combined Fourier transform microwave/millimeter-wave spectroscopic study of KSH (X{sup ~1}A{sup ′})

The pure rotational spectrum of KSH (X{sup ~1}A{sup ′}) has been measured using millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. This work is the first gas-phase experimental study of this molecule and includes spectroscopy of KSD as well. In the millimeter-wave system, KSH was synthesized in a DC discharge from a mixture of potassium vapor, H{sub 2}S, and argon; a discharge-assisted laser ablation source, coupled with a supersonic jet expansion, was used to create the species in the FTMW instrument. Five and three rotational transitions in the range 3–57 GHz were recorded with the FTMW experiment for KSH and KSD, respectively, in the K{sub a} = 0 component; in these data, potassium quadrupole hyperfine structure was observed. Five to six transitions with K{sub a} = 0–5 were measured in the mm-wave region (260–300 GHz) for the two species. The presence of multiple asymmetry components in the mm-wave spectra indicates that KSH has a bent geometry, in analogy to other alkali hydrosulfides. The data were analyzed with an S-reduced asymmetric top Hamiltonian, and rotational, centrifugal distortion, and potassium electric quadrupole coupling constants were determined for both isotopolgues. The r{sub 0} geometry for KSH was calculated to be r{sub S-H}more » = 1.357(1) Å, r{sub K-S} = 2.806(1) Å, and θ{sub M-S-H} (°) = 95.0 (1). FTMW measurements were also carried out on LiSH and NaSH; metal electric quadrupole coupling constants were determined for comparison with KSH. In addition, ab initio computations of the structures and vibrational frequencies at the CCSD(T)/6-311++G(3df,2pd) and CCSD(T)/aug-cc-pVTZ levels of theory were performed for LiSH, NaSH, and KSH. Overall, experimental and computational data suggest that the metal-ligand bonding in KSH is a combination of electrostatic and covalent forces.« less
Authors:
;  [1] ; ; ; ;  [2]
  1. Department of Chemistry and Biochemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, Arizona 85721 (United States)
  2. Department of Chemistry and Biochemistry, Canisius College, Buffalo, New York 14208 (United States)
Publication Date:
OSTI Identifier:
22251289
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 21; 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; ABLATION; ABSORPTION; CALCULATION METHODS; COUPLING CONSTANTS; FOURIER TRANSFORMATION; GHZ RANGE; HAMILTONIANS; HYDROGEN SULFIDES; HYPERFINE STRUCTURE; LIGANDS; MIXTURES; POTASSIUM; SPECTRA; SPECTROSCOPY