Site-selective photofragmentation of chlorinated polymeric films observed around the chlorine K-edge

► PVC and PVDC were studied by PSID and NEXAFS techniques at the Chlorine 1s-edge. ► PVC film presented isotope ratio of 3:1 in the PSID spectrum. ► Cl+ ion yield curves reproduce the photoabsorption spectrum for both polymers. ► Site-selectivity of C-Cl bond breaking due to an efficient spectator Auger decay.