Electron-molecule collisions with explicit rovibrational resolution at MRCI level and using even tempered basis sets.

Abstract

A method for calculating the generalized oscillator strengths (GOSs) and differential cross section (DCS) with vibration and rotation resolution is presented. The importance of accounting for the rotational contribution is to be emphasized since it has not previously been considered in GOS calculations. Although largely neglected due to its small effect on various properties, the rotational resolution proved to be fundamental in the study of certain phenomena, such as the interference between rotational states in a molecule. As the general goal of this work is to obtain theoretical values comparable to high resolution experiments, special care was taken on the calculation of the electronic part of the scattering amplitude, particularly in what concerns the choice of the atomic basis set. Accordingly, even-tempered basis sets have proved to lead to good results. The helium atom was taken as a model system for this aspect of the problem. Then, GOS and DCS, for explicit vibrational and rotational transitions, were calculated for hydrogen and nitrogen molecules. For higher accuracy, a non-Franck-Condon approach was used to obtain transitions involving vibrational states. The resultant values have shown good agreement with the available experimental data.