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

Abstract

Photon stimulated ion desorption (PSID) and Near-edge X-ray absorption fine structure (NEXAFS) studies have been performed on poly(vinyl chloride) (PVC) and poly(vinyl dichloride) (PVDC) around the chlorine 1s-edge. Experiments were performed using a synchrotron source operating in the single-bunch mode and a time-of-flight mass spectrometry for ion analysis. Cl+ ion yields, as a function of the photon energy, reproduce the photoabsorption spectrum, showing significant increase at the 1s-resonance. Edge-jump ratios, defined as the ratio between edge-jumps (intensity ratio of the yields between above and below the absorption edge) of two different transitions, for Cl+ ion yields were much higher than the equivalent electron yields, indicating site-selectivity in C–Cl bond breaking for both polymers, as a result of efficient spectator Auger decay. The expected isotope ratio of 3:1 for chlorine was measured for PVC. The interpretation of the NEXAFS spectrum was assisted by quantum mechanical calculations at a multireference perturbation theory level.