Spectroscopy of H3~+ with energies above the barrier to linearity: rovibrational transitions in the range of 10,000-14,000 cm~(-1)

摘要

Based on a recently extended potential energy surface for H_3~+ with a highly reliable form of the topology of the surface far beyond the barrier to linearity, rovibrational frequencies in the range of 10,000-14,000 cm~(-1) have been derived and are compared with new experiments. The computed transition frequencies reproduce experimental transitions mostly within a few tenths of a wavenumber, if non-adiabatic effects are crudely simulated using different reduced masses for vibrational and rotational motions. Deviations can only be compensated if non-adiabatic effects are treated more rigorously.