Calculation of Dyson orbitals using a symmetry-adapted-cluster configuration-interaction method for electron momentum spectroscopy: N2 and H2O.

The symmetry-adapted-cluster (SAC) configuration-interaction (CI) theory was introduced to interpret the non-coplanar symmetric (e,2e) results. Dyson orbitals derived from the bench-marked SAC CI general-R method were utilized for computing the electron momentum distributions. The corresponding excitation energies and spectroscopic factors can be used to reproduce the ionization spectra. The implementation was demonstrated by examples of N2 and H2O. The electron momentum distributions calculated using SAC CI method were compared with recent experimental results, as well as the Hartree-Fock and density-functional-theory calculations. The SAC CI method gave the best performance on the description of the experimental momentum distributions. It was found that the electron momentum distributions of Dyson orbitals related to the satellite lines can be notably different from those of their parent orbitals due to the electron correlation in the initial target states. Present work demonstrated that the SAC CI theory is a very useful and accurate tool for interpreting high-resolution electron momentum spectroscopy results. [ABSTRACT FROM AUTHOR]