THE MILLIMETER/SUBMILLIMETER SPECTRUM OF TiF$^{+}$ (X$^{3}\Phi_{r}$)
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Date
2006
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Ohio State University
Abstract
The pure rotational spectrum of the molecular ion TiF$^{+}$ (X$^{3}\Phi_{r}$) has been measured using a combination of millimeter-wave direct absorption methods and velocity modulation techniques. TiF$^{+}$ was created in an AC glow discharge using a mixture of gas-phase TiCl$_4$, 10\% F$_2$ in helium, and argon. In contrast to TiCl$^{+}$, the spectra of TiF$^{+}$ were weaker, a probable result of the synthesis method. Ten rotational transitions were measured in the frequency range of 327 to 542 GHz. All three spin-orbit components were observed, which were additionally split into doublets due to fluorine hyperfine interactions. The fine structure exhibited a regular case (a) pattern with minimal second-order spin-orbit effects. These data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The calculated bond length of TiF$^{+}$ was found to be shorter than that of TiF, which is thought to be due to an increase in the effective nuclear charge of titanium.
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Author Institution: Department of Chemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, AZ, 85721