Vibrational analysis of a Hylleraas-configuration interaction potential for H+3

Abstract

The potential surface for H+3, obtained from Hylleraas configuration interaction calculations by Frye et al. [J. Chem. Phys. 92, 4948 (1990)], has been fitted to a seventh-degree polynomial in Morse–Dunham coordinates to study the low-lying vibrational states of H+3, D+3, H2D+, D2H+, H2T+, and T2H+. Vibrational levels of up to two quanta excitations are reported and compared with experiments and other theoretical calculations. There are indications that adiabatic corrections may be important in correcting the small errors in the calculated vibrational quanta. The exothermicity of the proton-transfer reaction between H2 and H+2 predicted is 1.685 eV, to be compared with the experimental value of 1.7 eV. The calculated dissociation energy for H+3 is 4.337±0.002 eV, 355 cm−1 smaller than the experimental value of 4.381±0.021 eV. No source of discrepancy from theoretical side can be identified.