The photodissociation of Si-4 has been investigated using fast beam photofr
agment translational spectroscopy. The photofragment yield (PFY) spectrum s
hows features between 21370 and 22220 cm(-1) corresponding to the 1B(1u) --
> (X) over tilde (1)A(g) transition that are attributed to multi-photon dis
sociation. Single-photon dissociation was examined at higher excitation ene
rgies ranging from 5.17 to 6.42 eV. The dominant product channel was found
to be Si-3 + Si. Experimental photofragment translational energy distributi
ons were modeled by phase space theory (PST), indicating statistical photo
dissociation with no exit barrier along the dissociation coordinate. PST mo
deling yields a dissociation energy of 4.60 +/- 0.15 eV and DeltaH(f,0)(0)
(Si-4) = 6.75 +/- 0.24 eV. (C) 2001 Published by Elsevier Science B.V.