The He–H3+ complex. I. Vibration-rotation-tunneling states and transition probabilities

Abstract

With a He–[Formula: see text] interaction potential obtained from advanced electronic structure calculations, we computed the vibration-rotation-tunneling (VRT) states of this complex for total angular momenta J from 0 to 9, both for the vibrational ground state and for the twofold degenerate v2 = 1 excited state of [Formula: see text]. The potential has three equivalent global minima with depth D e = 455.3 cm−1 for He in the plane of [Formula: see text], three equatorial saddle points that separate these minima with barriers of 159.5 cm−1, and two axial saddle points with energies of 243.1 cm−1 above the minima. The dissociation energies calculated for the complexes of He with ortho-[Formula: see text] (o[Formula: see text]) and para-[Formula: see text] (p[Formula: see text]) are D0 = 234.5 and 236.3 cm−1, respectively. Wave function plots of the VRT states show that they may be characterized as weakly hindered internal rotor states, delocalized over the three minima in the potential and with considerable amplitude at the barriers. Most of them are dominated by the j k = 10 and 11 rotational ground states of o[Formula: see text] and p[Formula: see text], with the intermolecular stretching mode excited up to v = 4 inclusive. However, we also found excited internal rotor states: 33 in He–o[Formula: see text], and 22 and 21 in He–p[Formula: see text]. The VRT levels and wave functions were used to calculate the frequencies and line strengths of all allowed v2 = 0 → 1 rovibrational transitions in the complex. Theoretical spectra generated with these results are compared with the experimental spectra in Paper II [Salomon et al., J. Chem. Phys. 156, 144308 (2022)] and are extremely helpful in assigning these spectra. This comparison shows that the theoretical energy levels and spectra agree very well with the measured ones, which confirms the high accuracy of our ab initio He–[Formula: see text] interaction potential and of the ensuing calculations of the VRT states.