Dissociation of chloromethyltrimethylsilane (CMTMS) has been studied experimentally using 193 nm laser, and energetics of different channels have been obtained by ab initio MO calculations. A transient infrared emission, assigned to vibrationally excited HCl molecule, was observed, which was quenched by CMTMS with a rate constant of (1.2 +/- 0.1) x 10(-11) molecule(-1) cm(3) s(-1). Methane was found to be a major hydrocarbon product, and a thin transparent film was deposited on the entrance window. The results are compared with IR induced and plasma induced dissociation of this molecule. Transition state calculations indicate 1,2 Cl shift to Si with simultaneous migration of CH3, to be the lowest energy channel. (c) 2007 Elsevier B.V. All rights reserved.