Low-energy electron collisions with O2: Test of the molecularR-matrix method without diagonalization

Abstract

Electron collisions with O${}_{2}$ at scattering energies below 1 eV are studied in the fixed-nuclei approximation for a range of internuclear separations using the ab initio molecular R-matrix method. The ${}^{2}{\ensuremath{\Pi}}_{\mathrm{g}}$ scattering eigenphases and quantum defects are calculated. The parameters of the resonance and the energy of the bound negative ion are then extracted. Different models of the target that employ molecular orbitals calculated for the neutral target are compared with models based on anionic orbitals. A model using a basis of anionic molecular orbitals yields physically correct results in good agreement with experiment. An alternative method of calculation of the R matrix is tested, where instead of performing a single complete diagonalization of the Hamiltonian matrix in the inner region, the system of linear equations is solved individually for every scattering energy. This approach is designed to handle problems where diagonalization of an extremely large Hamiltonian is numerically too demanding.