Spectroscopic study of the F$^1\Sigma_g^+$ outer well state in H$_2$, HD and D$_2$

Abstract

Two-photon UV-photolysis of hydrogen sulfide molecules is applied to produce hydrogen molecules in highly excited vibrational levels in the \X\ electronic ground state, up to the dissociation energy and into the quasibound region. Photolysis precursors H$_2$S, HDS and D$_2$S are used to produce vibrationally hot H$_2$, HD and D$_2$. The wave function density at large internuclear separation is excited via two-photon transitions in the \F\ - \X\ system to probe ro-vibrational levels in the first excited \F\ outer well state of \emph{gerade} symmetry. Combining with accurate knowledge of the \X($v,J$) levels from advanced ab initio calculations, energies of rovibrational levels in the \F\ state are determined. For the H$_2$ isotopologue a three-laser scheme is employed yielding level energies at accuracies of $4 \times 10^{-3}$ \wn\ for F($v=0,J$) up to $J=21$ and for some low $J$ values of F($v=1$). A two-laser scheme was applied to determine level energies in H$_2$ for F($v=0-4$) levels as well as for various F levels in HD and D$_2$, also up to large rotational quantum numbers. The latter measurements in the two-laser scheme are performed at lower resolution and the accuracy is strongly limited to 0.5 \wn\ by ac-Stark effects. For H$_2$ a new quasibound resonance ($v=6$, $J=23$) is detected through the Q(23) and O(23) transitions in the F0-X6 band. The experimental results on F($v,J$) level energies are compared with previously reported theoretical results from multi-channel quantum-defect calculations as well as with results from newly performed nonadiabatic quantum calculations.