Angular distribution of molecular-field- and spin-orbit-split sulfur 2p photoemission in OCS: a sensitive probe of the molecular environment

Angle-resolved sulfur 2p photoelectron spectra from the OCS molecule are reported in very high electron and photon energy resolution. The measurements reveal significant differences in the angular distributions of ejected electrons associated with different core-level ionic multiplet states. A concomitant theoretical analysis relates these data to the perturbing effects of spin-orbit and molecular-field splittings, and indicates that the measured angular distributions in high resolution provide a new and sensitive probe of the molecular body-frame environment in the absence of explicit sample alignment.