ELECTRONIC SPECTROSCOPY AND VIBRATIONAL PREDISSOCIATION DYNAMICS OF OH/D-Kr

Author Institution: Department of Chemistry, Emory UniversityOH/D-Kr complexes were generated in expansion driven by Ne/Kr mixtures. Bands belonging to the complexes were seen in the vicinity of the OH/D A-X 0-0 and 1-0 transitions. Despite the congestion caused by presence of several Kr isotopes, seventeen bands were rotationally resolved and analyzed. For the ground state, the zero-point rotational constant defined a Kr to OH center of mass distance of 3.78$\pm$0.01 \AA. The relatively small effect of H/D isotopic substitution on the ground state rotational constant was consistent with a linear hydrogen-bonded equilibrium geometry. Assignment of the A state vibrational levels was accomplished by means of the Kr isotope effect. A lower limit for the dissociation energy for $OH(A, v=0)-Kr$ of $D_{e}>1840 cm^{-1}$ was derived from the vibrational constants. Extrapolation of the rotational constants yielded an equilibrium intermolecular separation of 2.67$\pm$0.12 \AA. Vibrational predissociation of OH/D(A, v=1)-Kr causes measurable line broadening in several bands. We are in the process of determining the linewidths, in order to quantify the predissociation rates. However, it is already evident that the linewidths do not show a simple dependence on internal energy, indicating the presence of novel dynamical effects. The results for OH/D-Kr will be compared and contrasted with those for OH/D-Ne and OH/D-Ar