ORBITAL MOMENTUM PROFILES AND BINDING-ENERGY SPECTRA FOR THE COMPLETEVALENCE SHELL OF MOLECULAR FLUORINE

The first electronic structural study of the complete valence shell bi nding energy spectrum of molecular fluorine, encompassing both the out er and inner valence regions, is reported. These binding energy spectr a as well as the individual orbital momentum profiles have been measur ed using an energy dispersive multichannel electron momentum spectrome ter at a total energy of 1500 eV, with an energy resolution of 1.5 eV and a momentum resolution of 0.1 a.u. The measured binding energy spec tra in the energy range of 14-60 eV are compared with the results of A DC(4) many-body Green's function and also direct-CI and MRSD-Cl calcul ations. The experimental orbital electron momentum profiles are compar ed with SCF theoretical profiles calculated using the target Hartree-F ock approximation with a range of basis sets and with Density Function al Theory predictions in the target Kohn-Sham approximation with non-l ocal potentials. The truncated (aug-cc-pv5z) Dunning basis sets were u sed for the Density Functional Theory calculations which also include some treatment of correlation via the exchange and correlation potenti als. Comparisons are also made with the full ion-neutral overlap ampli tude calculated with MRSD-Cl wavefunctions. Large, saturated basis set s (199-GTO) were employed for both the high level SCF near Hartree-Foc k limit and MRSD-Cl calculations to investigate the effects of electro n correlation and relaxation.