Rovibrational energy levels of H_3~+ with energies above the barrier to linearity

摘要

The H_3~+ potential energy surface is sampled at 5900 geometries with the emphasis on the nonequilibrium and asymptotic points. Apart from the Born_Oppenheimer energy converged to the accuracy better than 0.02 cm~(-1), the adiabatic and the leading relativistic corrections are computed at each geometry. To represent analytically the potential energy surface, the parameters of a power series are determined by fitting to the computed energy points. Possible choice of nuclear masses simulating the nonadiabatic effects in solving the nuclear Schr_dinger equation is analyzed. A set of theoretically predicted rovibrational transitions is confronted with the experimental data in the 10 700-13 700 cm~(-1) window of the spectra.