Velocity modulation spectroscopy of molecular ions I: The pure rotational spectrum of TiCl+ (X3Φr)

D. T. Halfen, Lucy M Ziurys

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The pure rotational spectrum of the TiCl+ ion in its X 3Φr ground state has been measured in the frequency range 323-424 GHz, using a combination of direct absorption and velocity modulation techniques. The ion was created in an AC discharge of TiCl 4 and argon. Ten, eleven, and nine rotational transitions were recorded for the 48Ti35Cl+, 48Ti37Cl+, and 46Ti 35Cl+ isotopomers, respectively; fine structure splittings were resolved in every transition. The rotational fine structure pattern was irregular with the Ω = 4 component lying in between the Ω = 2 and 3 lines. This result is consistent with the presence of a nearby 3Δr state, which perturbs the Ω = 2 and 3 sub-levels, shifting their energies relative to the Ω = 4 component. The data for each isotopomer were analyzed in a global fit, and rotational and fine structure parameters were determined. The value of the spin-spin constant was comparable to that of the spin-orbit parameter, indicating a large second-order spin-orbit contribution to this interaction. The bond length established for TiCl+, r0 = 2.18879 (7) Å, is significantly shorter than that of TiCl, which has r0 = 2.26749 (4) Å. The shorter bond length likely results from a Ti2+Cl- structure in the ion relative to the neutral, which is thought to be represented by a Ti +Cl- configuration. The higher charge on the titanium atom shortens the bond.

Original languageEnglish (US)
Pages (from-to)34-40
Number of pages7
JournalJournal of Molecular Spectroscopy
Volume234
Issue number1
DOIs
StatePublished - Nov 2005

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velocity modulation
rotational spectra
molecular ions
Modulation
Bond length
Spectroscopy
Ions
fine structure
Orbits
spectroscopy
Argon
Titanium
orbits
Ground state
ions
Atoms
alternating current
titanium
frequency ranges
argon

Keywords

  • Ions
  • Rotational
  • Spectroscopy

ASJC Scopus subject areas

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

Cite this

Velocity modulation spectroscopy of molecular ions I : The pure rotational spectrum of TiCl+ (X3Φr). / Halfen, D. T.; Ziurys, Lucy M.

In: Journal of Molecular Spectroscopy, Vol. 234, No. 1, 11.2005, p. 34-40.

Research output: Contribution to journalArticle

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N2 - The pure rotational spectrum of the TiCl+ ion in its X 3Φr ground state has been measured in the frequency range 323-424 GHz, using a combination of direct absorption and velocity modulation techniques. The ion was created in an AC discharge of TiCl 4 and argon. Ten, eleven, and nine rotational transitions were recorded for the 48Ti35Cl+, 48Ti37Cl+, and 46Ti 35Cl+ isotopomers, respectively; fine structure splittings were resolved in every transition. The rotational fine structure pattern was irregular with the Ω = 4 component lying in between the Ω = 2 and 3 lines. This result is consistent with the presence of a nearby 3Δr state, which perturbs the Ω = 2 and 3 sub-levels, shifting their energies relative to the Ω = 4 component. The data for each isotopomer were analyzed in a global fit, and rotational and fine structure parameters were determined. The value of the spin-spin constant was comparable to that of the spin-orbit parameter, indicating a large second-order spin-orbit contribution to this interaction. The bond length established for TiCl+, r0 = 2.18879 (7) Å, is significantly shorter than that of TiCl, which has r0 = 2.26749 (4) Å. The shorter bond length likely results from a Ti2+Cl- structure in the ion relative to the neutral, which is thought to be represented by a Ti +Cl- configuration. The higher charge on the titanium atom shortens the bond.

AB - The pure rotational spectrum of the TiCl+ ion in its X 3Φr ground state has been measured in the frequency range 323-424 GHz, using a combination of direct absorption and velocity modulation techniques. The ion was created in an AC discharge of TiCl 4 and argon. Ten, eleven, and nine rotational transitions were recorded for the 48Ti35Cl+, 48Ti37Cl+, and 46Ti 35Cl+ isotopomers, respectively; fine structure splittings were resolved in every transition. The rotational fine structure pattern was irregular with the Ω = 4 component lying in between the Ω = 2 and 3 lines. This result is consistent with the presence of a nearby 3Δr state, which perturbs the Ω = 2 and 3 sub-levels, shifting their energies relative to the Ω = 4 component. The data for each isotopomer were analyzed in a global fit, and rotational and fine structure parameters were determined. The value of the spin-spin constant was comparable to that of the spin-orbit parameter, indicating a large second-order spin-orbit contribution to this interaction. The bond length established for TiCl+, r0 = 2.18879 (7) Å, is significantly shorter than that of TiCl, which has r0 = 2.26749 (4) Å. The shorter bond length likely results from a Ti2+Cl- structure in the ion relative to the neutral, which is thought to be represented by a Ti +Cl- configuration. The higher charge on the titanium atom shortens the bond.

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