Abstract
The pure rotational spectrum of the molecular ion TiF+ in its 3Φr ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF+ was made in an AC discharge from a mixture of TiCl4, F2 in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl+, which is perturbed in the ground state. The data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF+, r0 = 1.7775 Å, was found to be shorter than that of TiF, r0 = 1.8342 Å-also established from mm-wave data. The hyperfine parameters determined are consistent with a δ1π1 electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF+ relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti2+F- configuration. A similar decrease in bond length was found for TiCl+ relative to TiCl.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 58-63 |
| Number of pages | 6 |
| Journal | Journal of Molecular Spectroscopy |
| Volume | 240 |
| Issue number | 1 |
| DOIs | |
| State | Published - Nov 2006 |
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Keywords
- Millimeter/submm spectroscopy
- Molecular ions
- Rotational
- Velocity modulation
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Spectroscopy
- Atomic and Molecular Physics, and Optics
Cite this
Velocity modulation spectroscopy of molecular ions II : The millimeter/submillimeter-wave spectrum of TiF+ (X3Φr). / Halfen, D. T.; Ziurys, Lucy M.
In: Journal of Molecular Spectroscopy, Vol. 240, No. 1, 11.2006, p. 58-63.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Velocity modulation spectroscopy of molecular ions II
T2 - The millimeter/submillimeter-wave spectrum of TiF+ (X3Φr)
AU - Halfen, D. T.
AU - Ziurys, Lucy M
PY - 2006/11
Y1 - 2006/11
N2 - The pure rotational spectrum of the molecular ion TiF+ in its 3Φr ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF+ was made in an AC discharge from a mixture of TiCl4, F2 in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl+, which is perturbed in the ground state. The data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF+, r0 = 1.7775 Å, was found to be shorter than that of TiF, r0 = 1.8342 Å-also established from mm-wave data. The hyperfine parameters determined are consistent with a δ1π1 electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF+ relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti2+F- configuration. A similar decrease in bond length was found for TiCl+ relative to TiCl.
AB - The pure rotational spectrum of the molecular ion TiF+ in its 3Φr ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF+ was made in an AC discharge from a mixture of TiCl4, F2 in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl+, which is perturbed in the ground state. The data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF+, r0 = 1.7775 Å, was found to be shorter than that of TiF, r0 = 1.8342 Å-also established from mm-wave data. The hyperfine parameters determined are consistent with a δ1π1 electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF+ relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti2+F- configuration. A similar decrease in bond length was found for TiCl+ relative to TiCl.
KW - Millimeter/submm spectroscopy
KW - Molecular ions
KW - Rotational
KW - Velocity modulation
UR - http://www.scopus.com/inward/record.url?scp=33750988754&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33750988754&partnerID=8YFLogxK
U2 - 10.1016/j.jms.2006.08.008
DO - 10.1016/j.jms.2006.08.008
M3 - Article
AN - SCOPUS:33750988754
VL - 240
SP - 58
EP - 63
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
SN - 0022-2852
IS - 1
ER -