The pure rotational spectrum of VS (X4Σ-): A combined Fourier transform microwave and millimeter-wave study

G. R. Adande, L. M. Ziurys

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

The pure rotational spectrum of the vanadium sulfide radical, VS (X 4Σ-), has been measured in the frequency range 5-310 GHz using a combination of millimeter-wave direct absorption and Fourier transform microwave (FTMW) techniques. In the millimeter-wave region, the radical was produced in an AC discharge from the reaction of VCl4, the vanadium donor, and CS2. In the FTMW instrument, the molecule was created in a supersonic jet, coupled with a laser ablation/DC discharge source (DALAS), from a mixture of metal vapor and H2S, heavily diluted in argon. A total of 8 rotational transitions were measured for VS, in which both the quartet fine structure and vanadium hyperfine splittings were resolved. The spectra were analyzed with a Hund's case (b) Hamiltonian, and rotational, spin-rotation, spin-spin, and hyperfine parameters were determined. The precision of the constants from previous optical studies was refined and, for the first time, the vanadium quadrupole constant, eQq = -7.6 (4.0) MHz, and the third order Fermi contact correction, bS = -0.293 (94) MHz, were established. From the fine structure parameters, the nearby 4Π and 2Σ+ states were estimated to lie ∼6560 cm -1 and ∼7170 cm-1 above the ground state. The hyperfine constants suggest that the bonding in VS is partly ionic, with a significant degree of covalent character.

Original languageEnglish (US)
Pages (from-to)42-47
Number of pages6
JournalJournal of Molecular Spectroscopy
Volume290
DOIs
StatePublished - Aug 23 2013

Keywords

  • FTMW spectroscopy
  • Hyperfine structure
  • Laser ablation
  • Millimeter wave spectroscopy
  • Vanadium sulfide (VS)

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Spectroscopy
  • Physical and Theoretical Chemistry

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