Photoinduced intracluster electron transfer reactions of captured intermediates in gas-phase SN2 reactions

摘要

We describe a series of experiments designed to establish the location of the charge-transfer excited states implied by the double minimum potential energy surface for the gas phase S$-N$/2 ion molecule reactions. Two distinguishable species, corresponding to the entrance and exit channel ion dipole complexes, are isolated in an ionized free jet. These complexes are interrogated by photodetachment spectroscopy in addition to the photoexcitation and collisional activation induced fragmentation patterns. Charged transfer excited states are evident in the X$+$MIN$/$PRM CH$-4$MIN@n$/Y$-n$/ (n $GREQ 2) species in which dissociative intra-cluster electron transfer yields XY$+$MIN$/ product ions while the S$-N$/2 reaction appears to be driven upon photoexcitation of the I$+$MIN$/$PRM CH$-3$/I complex.