dc.creator Harder, H. en_US dc.creator Macholl, S. en_US dc.creator Maeder, H. en_US dc.creator Fusina, L. en_US dc.creator Ozier, I. en_US dc.date.accessioned 2010-07-12T14:31:04Z dc.date.available 2010-07-12T14:31:04Z dc.date.issued 2010 en_US dc.identifier 2010-RC-11 en_US dc.identifier.uri http://hdl.handle.net/1811/46419 dc.description Author Institution: Institut fur Physikalische Chemie, Universitat Kiel, 24098; Kiel, Germany; Dipartimento di Chimica Fisica e Inorganica, Universita di; Bologna, 40136 Bologna, Italy; Department of Physics and Astronomy, University of British; Columbia, BC V6T 1Z1, Canada en_US dc.description.abstract For the principal isotopomer $^{14}$N$^{32}$S$^{19}$F$_{3}$ of thiazyl trifluoride in the degenerate fundamental state (\textit{v}$_{5}$=$1$), the hyperfine structure has been investigated in the \textit{Q}-branch spectrum between $8$ and $26.5$ GHz using microwave Fourier transform waveguide spectrometers with a resolution limit of $\approx 30$ kHz. In addition to $l$% -type doubling spectra and $l$-type resonance transitions with ($\Delta k$ =$% \Delta l$=$\pm 2$), perturbation-allowed spectra were measured with $\Delta$% ($k-l$) =$\pm 3$, $\pm 6$. The range in $J$ was from $13$ to $61$; for the lower states, $kl$=$-3$, $-2$, $-1$, $0$, $+1$. For all the transitions, the hyperfine patterns observed are predicted to be doublets when only the nitrogen quadrupole Hamiltonian \textbf{H}$_{Q}^{N}$ is taken into account. Doublets were indeed measured for transitions with $\Gamma _{RV}$=$% A_{1}\leftrightarrow A_{2}$, where $\Gamma _{RV}$ is the rovibrational symmetry. However, when $\Gamma _{RV}$=$E\leftrightarrow E$, triplets and quartets were observed in addition to doublets. These anomalous hyperfine patterns are shown to be due to the ($\Delta k$=$\pm 1$) and ($\Delta k$=$% \pm 2$) matrix elements of the fluorine spin-rotation Hamiltonian \textbf{H}$% _{N}^{F}$ characterized by the fluorine spin-rotation constants $% c(1)=(c_{xz}+c_{zx}^{\ast })$\ and $c(2)=(c_{xx}-c_{yy})$, respectively. These terms in \textbf{H}$_{N}^{F}$ lift the parity degeneracy for $\Gamma _{RV}$=$E$. The rovibrational Hamiltonian \textbf{H}$_{RV}$ was adopted from an earlier partner study. A good fit to the hyperfine data was obtained with a standard deviation of $3.1$ kHz. In the fitting process, $12$ rovibrational parameters were varied, while the remaining constants in \textbf{H}$_{RV}$ were left at the values of Ref. ($1$). In addition, $6$ hyperfine parameters were determined: four in \textbf{H}$_{Q}^{N}$, and two in \textbf{H}$_{N}^{F}$. It was found that $\leftert c(1)\rightert =7.48(24)$ kHz and $\leftert c(2)\rightert =2.423(22)$ kHz. This determination of $\leftert c(1)\rightert$ is the first to be reported based on frequency measurements. The key to the observation of the parity doubling lies in the severe mixing into the eigenvectors of basis vectors with several different values of $kl$ as a result of the clustering$^{1}$ of rovibrational levels at low $K$. en_US dc.language.iso en en_US dc.publisher Ohio State University en_US dc.title ANOMALOUS HYPERFINE STRUCTURE OF NSF$_{3}$ IN THE DEGENERATE VIBRATIONAL STATE $v_{5}$=1: LIFTING OF THE PARITY DEGENERACY BY THE FLUORINE SPIN-ROTATION INTERACTION en_US dc.type Article en_US dc.type Image en_US dc.type Presentation en_US
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