ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Dynamical processes accompanying the photofragmentation of (N2)+n clusters (n=3–6) have been investigated. Branching ratios for the formation of N+2 and N+4 photoproducts have been determined at wavelengths spanning the continuous absorption of the chromophore N+4 (630, 532, 396, 315, and 266 nm). In addition, the fraction of N+2 photofragments in excited vibrational states has been found using the monitor gas technique, whereby vibrationally excited N+2 molecules readily exchange charge with Ar buffer gas, and molecules in the υ=0 state do not. For a given sized cluster, as the photon energy increases, there is a trend towards a larger proportion of N+2 compared to N+4 fragments and a mild increase in the fraction of vibrationally excited N+2 fragments. On the other hand, as the size of the primary cluster grows, there is a growth in the proportion of N+4 fragments and a decrease in the fraction of vibrationally excited N+2 fragments. These features of (N2)+n cluster photodissociation are argued to be consistent with primary absorption by a N+4 chromophore core to form energetic N+2 and N2 fragments followed by efficient intracluster recombination, exchange of charge, and exchange of vibrational quanta. The efficiency of these processes for (N2)+3 and (N2)+4 suggest that in these species the N2 ligand(s) is (are) positioned at the end(s) of the linear N+4 ion core.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.465591
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