A nearly complete treatment of the effect of non-adiabaticity on rovibrational energies of H3+ (Part III)

Abstract

In this article, significant contributions of non-adiabaticity for the rovibrational bound states up to 25 000 cm−1 and total angular momentum J = 0–20 of H3+ are investigated. A coupled-perturbed full configuration interaction (CP-FCI) treatment is applied to calculate all couplings between electronic states caused by the nuclear motion. These derivative couplings were evaluated up to the second order by means of a perturbation treatment and include all nuclear Cartesian first and second derivatives of the electronic wavefunctions. In particular, the coupling of special derivatives with respect to r and R in the Jacobi coordinate representation is more significant than thought. The perturbation approach is especially optimal for the treatment of weak non-adiabaticity in case of rovibrational energies in H3+ and had not been available before for H3+ or other triatomics. Using exclusively Gaussian basis functions for CP-FCI appears to be sufficient, because explicit correlated wavefunctions are already used for all other potential energy contributions. Our work is an extension of earlier non-adiabatic investigations based on first derivative couplings of electronic states that led to the concept of geometry-dependent effective nuclear masses and which needs only a single potential energy surface for the dynamics. The implementation allows us to include all non-adiabatic effects up to the order of O(μ−2), μ being the reduced nuclear mass. Our treatment works for any isotopologue and for the whole potential energy curve or surface. By this treatment, a further reduction in deviations to experimental data for most rovibrational levels to less than 0.1 cm−1 is possible. For the related transition frequencies, 1366 of 1720 known rovibrational transitions in H3+ have deviations less than 0.1 cm−1 without using any empirically adjustable parameters or optimizing the nuclear mass for a specific transition. For many questionable assignments (deviations >0.3 cm−1) of observed transitions in H3+, a new labeling is proposed.