The Rydberg states of H 2 O

Empirical quantum defect functions are fit to the vibrational origins of the known rotationally resolved bands of H2O and D2O, including new analyses for bands in the region of the 3d (100) clusters. Consolidation of the H2O and D2O data allows an extrapolation of the 3p (0 v2 0) 1B2and 3p (1 v2 0) 1B2 linear state bending progressions as a means of rationalizing known perturbations and predissociations in the 3d clusters and of estimating their influence on the higher nd series. A new vibronic mechanism for autoionization from the 3d b11B1 linear state vibrational progression is found to be in excellent agreement with the observed autoionization rate.