Jd. Ewbank et al., TIME-RESOLVED GAS ELECTRON-DIFFRACTION STUDY OF THE 193-NM PHOTOLYSISOF 1,2-DICHLOROETHENES, Journal of physical chemistry, 97(34), 1993, pp. 8745-8751
We have employed time-resolved gas electron diffraction. using an exci
te-and-probe technique developed on the basis of various precedents,1-
2 for study of the 193-nm photodissociation of isomeric 1,2-dichloroet
henes. The procedure3 involves a pulsed electron beam synchronous with
photoexcitation and on-line electron diffraction intensity recording
with a photodiode array. When the time delay between excitation and di
agnostic electron scattering is 15 ns, only fragmentation and no cis-t
rans somerization is observed. When the time delay is several millisec
onds, cis-trans isomerization is prevalent. This finding confirms the
thesis that, because of faster intervening dissociative processes, cis
-trans isomerization is not a primary photochemically driven unimolecu
lar rearrangement of 193-nm irradiated dichloroethenes but hinges upon
intermolecular collisions.