P 1s spectroscopy of SPF3: spectral assignments aided by angle-resolved photodissociation

Symmetry-dependent P 1s excitation spectra of SPF3 have been obtained by performing photoelectron–photoion coincidence measurements with the ion detector oriented both parallel and perpendicular to the electric field vector of the exciting linearly polarized synchrotron radiation. The resulting total ion yield spectra and most of the partial fragment ion yield spectra show almost no polarization dependence. In contrast, the S+ and S2+ partial ion yield spectra do show a strong anisotropy, thereby providing clear evidence for the symmetries of the core-excited states and demonstrating the applicability of the axial-recoil approximation to a larger molecule than had been considered previously.