Chemiluminescence of dioxetanone investigated by self-consistent-field theory

Abstract

Abstract : SCF calculations using a 4-31G basis set were performed on dioxetanone. The results indicate that the four ring atoms of this peroxide are essentially coplanar. Also, stretching of the oxygen-oxygen bond does not lead to a concomitant increase in the carbon-carbon bond distance. This finding is taken to indicate that the thermal reaction of dioxetanone proceeds through a biradical. A rationalization of the very different yields of excited state products from dioxetane and dioxetanone is based upon this conclusion. The properties of the radial anion obtained by adding an electron to the 16a' orbital were probed computationally. It was found that increasing the oxygen-oxygen bond distance of the anion results in a remarkable decrease in energy. This finding is taken as support of the details of the chemically initiated electron-exchange luminescence (CIEEL) path suggested to be responsible for the majority of the chemiluminescence for dioxetanones. (Author)