Direct observation of silicon (3P) following state-selected photofragmentation of A 1B1 silylene

McKay, Ruth I.; Uichanco, Angelo S.; Bradley, Andrew J.; Holdsworth, John R.; Francisco, Joseph S.; Steinfeld, Jeffrey I.; Knight, Alan E. W.
August 1991
Journal of Chemical Physics;8/1/1991, Vol. 95 Issue 3, p1688
Academic Journal
The photophysics of silylene (SiH2), formed during the infrared multiphoton dissociation (IRMPD) of organosilanes, is investigated using photofragmentation excitation spectroscopy (PHOFEX). Silylene molecules are formed in the X 1A1(000) ground state via IRMPD of n-butylsilane. Laser induced fluorescence (LIF) is used to detect ground state (3p2 3P0) Si atoms following rovibronically resolved photoexcitation of SiH2 to the A 1B1(0v20) state. Variations in Si atom production are measured simultaneously with the SiH2 excitation spectrum, allowing comparisons to be made between Si yield and the rovibronic structure in the SiH2 1B1 manifold. We have examined the correlation between the widely varying fluorescence lifetimes of the individual rovibronic states of SiH2 and the relative yields of Si production. The presence of additional Si precursors in the primary dissociation process is suggested. Mechanisms for Si release following IRMPD of n-butylsilane and electronic excitation of SiH2 are developed and discussed.


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