Dynamical photoionization observables of the CS molecule: the role of electron correlation.

Highly correlated calculations are performed on the primary ionic states and the prominent satellite present in the outer valence photoelectron spectrum of carbon monosulfide (CS). Dyson orbitals are coupled to accurate one particle continuum orbitals to provide a correlated description of energy dependent cross sections, asymmetry parameters, branching ratios, and molecular frame photoelectron angular distributions. The comparison with results obtained at the Hartree-Fock and Density Functional Theory level shows the strong sensitivity of these observables to details of the correlation in the bound states. The behaviour of the well characterized satellite state is analyzed in detail, and shows differences from the relevant primary states, revealing the limitations of a simple intensity borrowing mechanism. The results resolve the intensity disagreement with experiment obtained at the level of the sudden approximation.