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

G. R. Adande, Lucy M Ziurys

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3 Citations (Scopus)

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 - 2013

Fingerprint

Vanadium
rotational spectra
Millimeter waves
millimeter waves
vanadium
Fourier transforms
Microwaves
microwaves
fine structure
Hamiltonians
metal vapors
Argon
Sulfides
Laser ablation
Ground state
laser ablation
sulfides
electric contacts
alternating current
quadrupoles

Keywords

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

ASJC Scopus subject areas

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

Cite this

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title = "The pure rotational spectrum of VS (X4Σ-): A combined Fourier transform microwave and millimeter-wave study",
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.",
keywords = "FTMW spectroscopy, Hyperfine structure, Laser ablation, Millimeter wave spectroscopy, Vanadium sulfide (VS)",
author = "Adande, {G. R.} and Ziurys, {Lucy M}",
year = "2013",
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T1 - The pure rotational spectrum of VS (X4Σ-)

T2 - A combined Fourier transform microwave and millimeter-wave study

AU - Adande, G. R.

AU - Ziurys, Lucy M

PY - 2013

Y1 - 2013

N2 - 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.

AB - 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.

KW - FTMW spectroscopy

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KW - Laser ablation

KW - Millimeter wave spectroscopy

KW - Vanadium sulfide (VS)

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