A supersonic free jet expansion has been used to prepare trans-stilbene--H2 and D2 complexes. The cooling in the jet collapses most of the ortho and para H2 and D2 rotational population to the lowest rotational levels of a given nuclear spin symmetry: j = 0 and j = 1. The laser-induced fluorescence excitation spectrum of stilbene--D2 shows a well-resolved doublet at the origin due to stilbene--D2( j = 0) and stilbene--D2( j = 1) complexes. The 4.9 cm-1 splitting of these transitions indicates that the D2 molecule is undergoing hindered internal rotation in the complex and that the barrier to internal rotation changes upon electronic excitation. The relative intensities of the stilbene--D2( j = 0) and stilbene--D2( j = 1) origins depend on the D2concentration in the jet. At low D2 flows the transitions arising from stilbene--D2( j = 1) are favored while at high D2 flows the ( j = 0)/(j = 1) transition intensities approach the 2:1 intensity ratio given by their nuclear spin statistical weights. By contrast, in stilbene--H2 we observe only a single transition at the origin which we assign to stilbene--H2( j = 1). We are able to place an upper bound on the stilbene--H2( j = 0) transition intensity of 5% of the stilbene--H2( j = 1) intensity. Dispersed fluorescence spectra are used to bracket the binding energies of the stilbene--H2/D2 complexes in both ground and excited states.
Digital USD Citation
De Haan, David O. and Zwier, Timothy S., "Hindered Internal Rotation and Ortho-H2 Enrichment in Trans-Stilbene--H2/D2 Complexes" (1989). Chemistry and Biochemistry: Faculty Scholarship. 1.