ROTATIONAL SPECTRUM AND INTERNAL DYNAMICS OF THE $Ne-H_{2}S$ VAN DER WAALS COMPLEX

$^{a}$H. S. Gutowsky, T. Emilsson, and E. Arunan, J. Chem. Phys. 106, 5309 (1997). $^{b}$G. de Oliveria and C. Dykstra, J. Chem. Phys. 110, 289 (1999).Author Institution: University of Alberta; Department of Chemistry, University of AlbertaRotational spectra of several isotopomers of the $Ne-H_{2}S$ van der Waals dimer were measured in the frequency range from 4 to 22 GHz, using a pulsed molecular beam Fourier transform microwave spectrometer. Two $K=0$ progressions were recorded for the symmetrical isotopomers (with $H_{2}S/D_{2}S$). This doubling is attributed to an internal rotation motion of the $H_{2}S$ moiety within the complex. The two states can be correlated to the $0_{00}$ and $1_{01}$ internal rotor states of free $H_{2}S$ and $D_{2}S$. Only one $K=0$ progression was measured for $Ne-DSH$. The excited internal rotor state is no longer metastable since the symmetry constraints no longer apply. An anomalous isotope effect observed in $Ar-H_{2}S$, where the substitution of hydrogen by deuterium causes an increase in the ground state B rotational $constant,^{a}$ was not observed here, in agreement with the ab initio study by $Dykstra and co-workers.^{b}$ Nuclear quadrupole hyperfine structure was resolved or partially resolved for isotopomers containing $^{33}S$ and $D$, respectively, and the corresponding quadrupole coupling constants were determined. These were used to derive information about the intermolecular dynamics. The results are compared with those of $Ar-H_{2}S$ and $Ar-H_{2}O$