1996 POLANYI-AWARD-LECTURE PROTON REACTIONS IN CLUSTERS

Reactions in mesoscopic, molecular clusters may proceed by mechanisms and with rates that differ from those in bulk solvents. Two examples o f reactions in large, liquid-state, molecular clusters are described t o illustrate the distinctive features of these reactions: acid dissoci ation and proton transfer in aprotic, polar solvents. Both of these re actions involve proton dynamics so methods for dealing with mixed quan tum-classical systems must be utilized to investigate the reaction dyn amics. Surface versus bulk solvation effects play an important role in determining the reaction mechanisms as do the strong cluster fluctuat ions. Mechanisms for proton transfer within clusters that have no bulk analogs will be described.