Millimeter/submillimeter-wave spectrum of the VCl+ radical in its X 4Σ- ground state

D. T. Halfen, Lucy M Ziurys

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The pure rotational spectrum of the molecular ion VCl+ (X 4Σ-) has been recorded from 274 to 419 GHz using a combination of millimeter direct absorption and velocity modulation spectroscopy. This study is the first spectroscopic measurement of this species in the laboratory, which has also enabled the determination of the ground state term, 4Σ-. VCl+ was produced in an AC discharge of VCl4 and argon. Fifteen and eleven rotational transitions were recorded for the V35Cl+ and V 37Cl+ isotopologues, respectively. The fine structure splittings of the 4Σ- state were found to deviate significantly from a case (b) pattern. Specifically, spin components from adjacent rotational transitions were found to overlap in frequency. Unusual vanadium hyperfine splittings were also observed in the VCl+ spectra; the expected vanadium octet was clearly present for the F2 and F3 spin components but was partially collapsed and reversed in frequency ordering in the F1 and F4 cases. The data were analyzed in a global fit, and rotational, fine structure, and hyperfine constants were determined. For VCl+, the values of both the spin-spin and spin-rotation parameters are extremely large, as were the third-order hyperfine and spin-rotation terms, bs and γs. For example, the spin-spin constant is a = 417 900(22 700) MHz, while γ = 6567(51) MHz. The values of these constants indicate a high density of excited electronic states close to the ground state, which contribute to second and third-order spin-orbit coupling. The hyperfine constants suggest a s1p2 electron configuration, as opposed to s1d2, as found in VS and VO. The bond length of VCl+, r0 = 2.119(2) Å, is shorter than that of VCl by 0.1 Å, which has r0 = 2.219 Å. The decrease in bond length is attributed to an increase in the electrostatic attraction between V2+ and Cl-, as opposed to V+ and Cl - for VCl.

Original languageEnglish (US)
Pages (from-to)13436-13442
Number of pages7
JournalJournal of Physical Chemistry A
Volume113
Issue number47
DOIs
StatePublished - 2009

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Submillimeter waves
Vanadium
submillimeter waves
Bond length
Millimeter waves
Ground state
ground state
Argon
Electronic states
Electrostatics
Orbits
Modulation
Spectroscopy
Ions
Electrons
vanadium
fine structure
velocity modulation
octets
rotational spectra

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Millimeter/submillimeter-wave spectrum of the VCl+ radical in its X 4Σ- ground state. / Halfen, D. T.; Ziurys, Lucy M.

In: Journal of Physical Chemistry A, Vol. 113, No. 47, 2009, p. 13436-13442.

Research output: Contribution to journalArticle

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title = "Millimeter/submillimeter-wave spectrum of the VCl+ radical in its X 4Σ- ground state",
abstract = "The pure rotational spectrum of the molecular ion VCl+ (X 4Σ-) has been recorded from 274 to 419 GHz using a combination of millimeter direct absorption and velocity modulation spectroscopy. This study is the first spectroscopic measurement of this species in the laboratory, which has also enabled the determination of the ground state term, 4Σ-. VCl+ was produced in an AC discharge of VCl4 and argon. Fifteen and eleven rotational transitions were recorded for the V35Cl+ and V 37Cl+ isotopologues, respectively. The fine structure splittings of the 4Σ- state were found to deviate significantly from a case (b) pattern. Specifically, spin components from adjacent rotational transitions were found to overlap in frequency. Unusual vanadium hyperfine splittings were also observed in the VCl+ spectra; the expected vanadium octet was clearly present for the F2 and F3 spin components but was partially collapsed and reversed in frequency ordering in the F1 and F4 cases. The data were analyzed in a global fit, and rotational, fine structure, and hyperfine constants were determined. For VCl+, the values of both the spin-spin and spin-rotation parameters are extremely large, as were the third-order hyperfine and spin-rotation terms, bs and γs. For example, the spin-spin constant is a = 417 900(22 700) MHz, while γ = 6567(51) MHz. The values of these constants indicate a high density of excited electronic states close to the ground state, which contribute to second and third-order spin-orbit coupling. The hyperfine constants suggest a s1p2 electron configuration, as opposed to s1d2, as found in VS and VO. The bond length of VCl+, r0 = 2.119(2) {\AA}, is shorter than that of VCl by 0.1 {\AA}, which has r0 = 2.219 {\AA}. The decrease in bond length is attributed to an increase in the electrostatic attraction between V2+ and Cl-, as opposed to V+ and Cl - for VCl.",
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