Photodissociation of 2,2-diphenylhexamethyltrisilane (dphmts) has been investigated in the range from 262 to 275 nm in a supersonic molecular beam. From the excitation spectrum, the S, origin band was determined as 36419 cm(-1). We have observed the parent ion, Ph2Si(SiMe3)(2)(+) and its various daughter ions of Ph2SiSiMe+, Ph2SiMe+, PhSiSiMe3+, PhSiSiMe2+,PhSiMe2+, PhSi+, and SiMe3+ Occurrences of consecutive bond scissions and rearrangements with excess energy accurnulated by additional photon absorption after the two-photon ionization of dphmts molecule could explain the formation of the various ionic products. (c) 2005 Elsevier B.V. All rights reserved.