A Mechanistic Study of Thermal Decomposition of 1,1,2,2-Tetramethyldisilane Using Vacuum Ultraviolet Photoionization Time-of-Flight Mass Spectrometry

Thermal decomposition of 1,1,2,2-tetramethyldisilane was performed by flash pyrolysis in a SiC microreactor in the temperature range from 295 to 1340 K, followed by molecular beam sampling and vacuum ultraviolet photoionization mass spectrometry analysis. Density functional theory investigations on the energetics of reactants, intermediates, and products were carried out to support the experimental observations. Energetics for 1,1,2,2-tetramethyldisilane initiation decomposition reactions and important secondary reactions were calculated. Dimethylsilane, dimethylsilyl radicals, dimethylsilylene, trimethylsilane, and tetramethyldisilene were determined as the primary reaction products in the initiation thermal decompositions of 1,1,2,2-tetramethyldisilane. Further decomposition reactions of tetramethyldisilene, such as production of dimethylsilene (m/z = 72) and eventually SiC₃H₄ (m/z = 68) fragments, were examined. Other products from secondary reactions of dimethylsilane and dimethylsilylene such as SiC₂H_2-6 and SiCH_0-4 were also observed. The comprehensive pyrolysis mechanism of 1,1,2,2-tetramethyldisilane was proposed.