Potential curves and nonadiabatic matrix elements for collisions involving fragments of the HeN+ molecular ion

Abstract

Ab initio multireference CI calculations have been carried out for the HeN+ molecular ion in order to describe collision processes between its constituent neutral and ionized atoms. The accuracy of these calculations is evaluated by means of a comparison of results obtained at large internuclear separations with the corresponding asymptotic energies deduced from atomic spectral data. Energy values are computed for the eleven lowest He++N and He+N+ atomic limits and average discrepancies relative to the experimental excitation energies up to 110 000 cm−1 are found to lie in the 1000–3000 cm−1 range, of which only 200 cm−1 appears to be the fault of the configuration interaction (CI) technique itself, with the main portion of the error stemming from the choice of atomic orbital (AO) basis instead. The HeN+ X 3Σ− ground state is calculated to have a De value of only 1414 cm−1, but the excited 2 3Π state has a much larger value of 22 133 cm−1 by virtue of an avoided crossing with the lower state of this symmetry. The corresponding radial nonadiabatic coupling is responsible for a large cross section for an excitation process between the N+(3Pg)+He and N+(3Du)+He channels which indirectly provides an efficient electron-capture mechanism leading to the N(4Su)+He+ exit channel. Additional nonadiabatic matrix elements for rotational and spin–orbit coupling have also been obtained and analyzed, as well as transition moments between the various HeN+ molecular states calculated.