High density chemiluminescence studies: explosive decomposition of solid phase tetramethyldioxetane

Abstract

Abstract The spectral and temporal profiles of the chemiluminescence resulting from IR-laser-induced decomposition of solid phase tetramethyldioxetane (TMD) are reported. An unusual two-component luminescence signal is observed. The first component at 0 – 10 μs is shown to evolve from the initially laser-heated portion of the TMD crystal. The second component at 30 – 500 μs arises from the explosion of the crystal bulk induced by heat released during the decomposition of the skin. Kinetic modeling of the decomposition results in good agreement of the calculated and experimental time scales for decomposition. The modeling studies suggest that an autocatalytic chain reaction is important in the decomposition mechanism. The two emission components are shown to have the same visible spectrum which peaks at 410 nm and has a full width at half-maximum of 30 – 50 nm. The results suggest that excited state singlet acetone is the species responsible for both components of the emission.