Benzyl alcohol/ammonia, agr;,agr;hyphen;dimethylbenzyl alcohol/ammonia, and benzyl alcohol/water cluster ion fragmentation and chemistry are studied for isolated cold clusters by means of one and twohyphen;color mass resolved excitation spectroscopy, nozzle/laser timing delay, and deuteration experiments. Experiments lead to an identification of parent clusters for all fragment ion clusters observed. Three types of cluster ion fragmentation are observed for these systems: dissociationminus;solu+(solv)nrarr;solu+(solv)k+msolv; acidhyphen;base chemistryminus;ArCH2OH+(B)nrarr;ArCH2O(B)k+BmH+; and (benzyl) radical chemistryminus;ArCH2OH+(B)nrarr;ArCdot;HOH(B)k+BmH+, ArCD2OH+(B)nrarr;ArCDHOH+(B)k+BmBminus;d2and ArCMe2OH+(B)nrarr;ArCdot;MeOH+(B)k+BmMdot;e. Fragmentation reactions depend on cluster size, structure, and (weakly) on the vibrational energy deposited in the ion. Specifically, for benzyl alcohol+(NH3)1only cluster radical chemistry and dissociation take place, while for higher order clusters, the acidhyphen;base reaction rate increases and this reaction becomes a major fragmentation pathway for benzyl alcohol+(NH3)4. For the benzyl alcohol(H2O)nsystem, cluster radical chemistry is not observed withn=1, only a weak agr;hyphen;hydrogen transfer reaction is observed withn=2, and acid base chemistry is not observed for clusters of any size. Cluster dissociative fragmentation is also a function of cluster size; large water and ammonia clusters dissociate much more easily than don=1 clusters. The possible mechanisms for these fragmentation patterns are discussed.
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